The Degradation Mechanism of Multi-Resonance Thermally Activated Delayed Fluorescence Materials

The Degradation Mechanism of Multi-Resonance Thermally Activated Delayed Fluorescence Materials | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article The Degradation Mechanism of Multi-Resonance Thermally Activated Delayed Fluorescence Materials Youngmin You, Byung Hak Jhun, Hwang Suk Kim, Joonghyuk Kim, Yerin Park, and 6 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4184912/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 04 Jan, 2025 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Abstract 1,4-Azaborine-based arenes gained prominence as electroluminescent emitters that exhibit thermally activated delayed fluorescence (TADF). These materials display exceptionally narrow emission spectra and high photoluminescence quantum yields, benefits arising from the multi-resonance (MR) effect. The practical application of MR-TADF emitters is often constrained by their limited operational stability. In this study, we explore the mechanism responsible for the degradation of a series of MR-TADF molecules. Electroluminescent devices employing these compounds show varied operational lifetimes, which do not align with either the excitonic stability of the emitter molecules or the degree of roll-off in external quantum efficiency. Our bulk electrolysis study reveals a considerable instability of the radical cationic forms of the MR-TADF compounds. A direct correlation is observed between device lifetime and the Faradaic yield for oxidative degradation of the emitter molecules. Comprehensive chemical analyses suggest that the degradation byproducts originate from intramolecular cyclization in the radical cation, preceded by intermolecular hydrogen atom transfer. Quantum chemical calculations indicate that this intramolecular cyclization accelerates the overall reaction, implying that cyclization reactivity is crucial for the intrinsic stability of the MR-TADF compound upon hole trapping. Our study offers an explanation for the beneficial effects of deuteration on the intrinsic stability and lays the groundwork for developing mechanism-based strategies to design MR-TADF compounds with greater operational longevity. Physical sciences/Materials science/Materials for optics/Lasers, LEDs and light sources/Organic LEDs Physical sciences/Chemistry/Materials chemistry/Optical materials Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Introduction Organic light-emitting devices (OLEDs) have undergone significant advancements over the past two decades, with notable improvements in efficiency and color purity. These advances are largely due to the discovery of novel emitters, including luminescent molecules capable of exciton harvesting. Among these, cyclometalated complexes of Ir(III) 1,2 and Pt(II) 3,4 , as well as organic 5,6 and organometallic compounds 7,8 that exhibit thermally activated delayed fluorescence (TADF), stand out. The multi-resonance (MR)-TADF emitters, in particular, have attracted considerable attention. For instance, aromatic 1,4-azaborine scaffolds housing complementary boron and nitrogen atoms produce exceptionally narrow fluorescence spectra, accompanied with photoluminescence quantum yields approaching unity. 9-11 The unique emission behavior positions MR-TADF compounds as promising candidates for meeting the demanding requirements of commercial OLED applications. 12-17 Despite their potential, the widespread adoption of MR-TADF molecules is hampered by their instability under the operational conditions in the device. This issue is not unique to MR-TADF molecules. It mirrors challenges faced by earlier generations of phosphorescent and dipolar TADF emitters, 18-25 which also degrade through mechanisms that produce exciton quenchers, charge carrier traps, and non-emissive charge carrier recombination centers, adversely affecting OLED performance. Consequently, a deeper understanding of the degradation mechanisms of MR-TADF materials is crucial for enhancing their operational longevity. Notably, Lee et al . discovered that TADF-inactive MR fluorescent emitters could achieve longer operational lifetimes than their TADF-active counterparts, 26 a finding echoed by Meng et al. , 27 who attributed this to the intrinsic instability of long-lived triplet excitons in MR-TADF emitters. In-situ Raman spectroscopy studies suggested that MR-TADF excitons contribute to the morphological instability of emitting layers. 28 Furthermore, Wang et al . have shown that incorporating an additional boracycle into MR-TADF emitters can extend operational lifetimes, a benefit theorized to stem from increased anionic stability, as supported by quantum chemical calculations. 29 While these studies have proposed various factors contributing to reduced operational lifetimes, direct chemical evidence identifying the specific intermediates and pathways of degradation remains scarce. Given that an OLED’s operational lifetime is primarily determined by the intrinsic stability of its components, 30 elucidating the degradation process of MR-TADF molecules is of paramount importance. In this study, we delve into the intricate chemical mechanisms underlying the intrinsic degradation of a series of blue-emissive MR-TADF molecules, as illustrated in Fig. 1. Through comprehensive chemical analyses, we obtained direct experimental evidence indicating that the primary degradation pathway of MR-TADF materials is initiated by hole trapping. Both experimental observations and quantum chemical computer simulations suggest that the degradation process involves a dehydrogenative cyclization reaction of the radical cationic species. This novel mechanism elucidates the observed enhanced operational stability of a deuterated MR-TADF emitter compared to its undeuterated counterpart, attributing it to the slower dehydrogenative cyclization due to the kinetic isotope effect in the deuterated molecule ( vide infra ). Results Operational stabilities of MR-TADF OLEDs For this investigation, we selected 5,9-bis(4-biphenyl)-2,12-diphenyl-5,9-diaza-13b-boranaphtho[3,2,1- de ]anthracene ( 1 ), N 7 , N 7 , N 13 , N 13 ,5,9,11,15-octaphenyl-5,9,11,15-tetrahydro-5,9,11,15-tetraaza-19b,20b-diboradinaphtho[3,2,1- de :1',2',3'- jk ]pentacene-7,13-diamine ( ν -DABNA 10 and denoted as 2 in this study), 5,9-bis(4-biphenyl)-7- N -(2-biphenyl)- N -(4-biphenyl)amino-2,12-diphenyl-5,9-diaza-13b-boranaphtho[3,2,1- de ]anthracene ( 3 ), and 5,9-bis(4- tert -butylphenyl)-2,12-di( tert -butyl)-5,9-diaza-13b-boranaphtho[3,2,1- de ]anthracene ( t -DABNA 31 and denoted as 4 in this study) shown in Fig. 1 . The photophysical characteristics of these compounds were assessed using thick films of poly(methyl methacrylate) (PMMA) doped with 2 wt % of the MR-TADF compounds, and the results are summarized in Table 1 . Compounds 1−4 displayed pronounced blue fluorescence, with emission peak wavelengths ranging from 459 to 471 nm, full widths at half-maximum (FWHM) values between 775 and 1130 cm −1 , and photoluminescence quantum yields ( Φ PL ) from 0.96 to 1.00. The delayed fluorescence lifetimes ( τ DF s) of these compounds span from 3.8 to 111 microseconds, indicative of moderate energy differences between the singlet and triplet excited states (Δ E ST , 0.11−0.27 eV). These photophysical parameters collectively underscore the MR-TADF properties of compounds 1−4 . Table 1 Photophysical and electrochemical data, and yields for intrinsic degradation of the MR-TADF dopants λ eµ (nm) a , b Φ PL (%) a , c τ PF (ns) a , d τ DF (µs) a , e k r TADF (10 4 s −1 ) f E T1 (eV) a , g Δ E ST (eV) a , h E ox (V vs SCE) i Φ deg (%) j Faradaic yield (%) k 1 471 96 11 78 5.1 2.49 0.27 0.98 0.29 37 2 467 98 6 3.8 6.3 2.64 0.11 0.92 0.92 46 3 461 98 7 28 5.6 2.57 0.21 0.97 0.68 59 4 459 100. 5 111 5.4 2.54 0.25 0.90 0.22 79 a 2 wt % in PMMA films, 300 K. See Supplementary Fig. 1 for the UV−Vis absorption and photoluminescence spectra recorded in tetrahydrofuran (THF). b Emission peak wavelength. See Supplementary Fig. 2 for the photoluminescence spectra of the PMMA films. c Photoluminescence quantum yield determined absolutely using an integrating sphere. d Lifetime of prompt fluorescence. e Lifetime of delayed fluorescence. f Radiative rate constant, k r TADF = Φ PL / τ obs , where τ obs is the average fluorescence lifetime. g Energy of the triplet state. h The energy difference between the singlet and the triplet excited states. Refer to Supplementary Fig. 3 for details. i Oxidation potential determined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) for Ar-saturated THF containing 1.0 mM dopant and 0.10 M tetrabutylammonium hexafluorophosphate; A glassy carbon disk and a Pt wire for the working and counter electrodes, respectively; a Ag/AgNO 3 pseudo reference electrode; scan rates = 0.1 V s −1 (CV) and 4 mV s −1 (DPV). See Supplementary Fig. 4 for the voltammograms. j Quantum yield for photolysis. k Faradaic yield for oxidative bulk electrolysis. The electroluminescence performances of compounds 1−4 , utilized as dopants, were assessed using a specific device configuration, comprising an indium tin oxide (ITO) anode, a hole-injection layer of p -doped (3 wt% NDP series, Novaled AG) N -([1,1′-biphenyl]-4-yl)-9,9-dimethyl- N -(4-(9-phenyl-9 H -carbazol-3-yl)phenyl)-9 H -fluoren-2-amine (BCFA) (10 nm), a hole-transporting layer of BCFA (135 nm), an electron-blocking layer of 2,2′-di(9 H -carbazole-9-yl)-1,1′-biphenyl (oCBP) (5 nm), an exciton-blocking layer of 3′,5′-di-9 H -carbazol-9-yl-[1,1′-biphenyl]-2-carbonitrile (mCPD) (5 nm), an emission layer (40 nm), a hole-blocking layer of 9-(3-(9 H -carbazol-9-yl)phenyl)-9 H -carbazole-3,6-dicarbonitrile (mCP-2CN) (10 nm), an electron-transporting layer co-deposited with dibenzo[b,d]furan-2,8-diylbis(diphenylphosphine oxide) (DBFPO) and lithium 8-hydroxyquinolinate (LiQ) (22 nm), an electron-injecting layer of LiQ (9 nm), and an aluminum (Al) cathode (100 nm). The emission layer, comprising a 1.5 wt % dopant, utilized a ternary composition including a 9-(3-biphenyl)-3,9′-bicarbazole hole-transporting (HT) host, a 3′-(9-(3-cyanocarbazolyl))-5′-cyano-3-(9-carbazolyl)biphenyl electron-transporting (ET) host, in a volumetric ratio of 6:4. The chemical structures and energy levels of the constituent materials are displayed in Fig. 2 a. Electroluminescence spectra, recorded at an intensity of 1000 cd m −2 , revealed peak wavelengths of 474 nm for compounds 1 and 2 , 465 nm for compound 3 , and 462 nm for compound 4 , as shown in Fig. 2 b. The FWHM values as small as 890−1300 cm −1 and the Commission internationale de l'éclairage coordinate y values (CIE y ) approaching 0.10 demonstrate the validity of the MR-TADF molecules as blue emitters. The devices incorporating 1−4 demonstrate negligible differences in their current density profiles, as depicted in Fig. 2 c. This uniformity can be attributed to the similar energy offsets between the highest occupied molecular orbitals (HOMOs) of 1−4 and the HT host ranging from 0.4 to 0.5 eV. The maximum external quantum efficiency ( EQE max ) across these devices is identified to lie between 22.5 and 26.7% (Table 2 ). Figure 2 d reveals that devices based on compounds 1 , 3 , and 4 experience moderate EQE roll-off, whereas the device utilizing compound 2 shows a relatively suppressed roll-off due to the significantly shorter delayed fluorescence lifetime ( τ DF ) of 3.8 µs, compared to 28−111 µs for the other MR-TADF compounds. These varying roll-off profiles hint at the presence of triplet−triplet annihilation or triplet−polaron annihilation processes, which are recognized for generating unstable species that shorten device operational lifetimes. 30,32,33 Nonetheless, there appears to be no direct correlation between the operational stability and EQE roll-off behaviors (Fig. 2 e). For instance, devices of 1 and 3 , despite showing substantial EQE roll-off, exhibit LT 95 (the time at which luminance decreases to 95% of its initial value at 1000 cd m −2 ) values of 4.3 and 2.9 h, respectively, comparable to the 3.2 h of device 2 that has the least EQE roll-off. Moreover, device 4 , despite having an EQE roll-off profile similar to that of devices 1 and 3 , presents the shortest LT 95 value of only 0.6 h. This observation suggests that the lifetime of these devices may not be predominantly determined by the bimolecular annihilation processes involving excitons. Table 2 Device performance V (V) a J (mA cm −2 ) a CIE (x, y) a EQE (%) power efficiency (lm W −1 ) LT 95 (h) c 1 5.14 7.00 (0.11, 0.17) 25.1 b / 12.3 a 30.9 b / 8.79 a 4.3 2 5.38 5.75 (0.11, 0.15) 23.7 b / 17.4 a 21.3 b / 10.2 a 3.2 3 5.25 5.25 (0.13, 0.11) 26.7 b / 16.8 a 24.5 b / 9.19 a 2.9 4 6.11 6.11 (0.13, 0.10) 22.5 b / 5.8 a 20.0 b / 2.57 a 0.60 a Values at a luminance of 1000 cd m −2 . b Maximum values. c Operation time when the luminance decreases to 95% of its initial value at initial luminance of 1000 cd m − 2 . See Supplementary Fig. 5 for plots of the luminance and power efficiency as functions of current density. Degradation intermediates To elucidate the degradation mechanisms of MR-TADF dopants, we conducted both photolysis and bulk electrolysis experiments. These experiments aimed to simulate the excitonic and polaronic degradation pathways, respectively, facilitating the identification of crucial degradation intermediates. Photolysis was performed in argon-saturated tetrahydrofuran (THF) solutions containing 100 µM of compounds 1 − 4 , under continuous illumination with monochromatic light of 450 nm wavelength (photon flux = 4.0 × 10 8 einstein s − 1 ). The progression of photolytic degradation was monitored using high-performance liquid chromatography (HPLC) due to the inadequacy of UV − Vis absorption spectroscopy for quantitative analysis. The quantum yield for degradation ( Φ deg ) was determined to be under 1% (Table 1 and Fig. 3 c), and importantly, Φ deg exhibited no significant correlation with LT 95 , suggesting that unimolecular excitonic degradation does not primarily influence the operational stability (for additional details and discussion, see Supplementary Fig. 6). In marked contrast, radical cation forms of the MR-TADF molecules demonstrated pronounced instability during oxidative bulk electrolysis at anodic potentials, as quantified by HPLC (detailed in Fig. 3 a, 3 b, and their captions). Reductive bulk electrolysis was not considered, given the electron-scattering nature of the MR-TADF molecules, as inferred from the positions of their lowest unoccupied molecular orbitals (LUMOs) illustrated in Fig. 2 a. By contrast, the MR-TADF compounds can trap hole carriers from the HT host with driving forces of 0.4−0.5 eV. The Faradaic yields for oxidative bulk electrolysis, representing the ratio of decomposed compound quantity to the electrons transferred, were significantly higher by two orders of magnitude compared to Φ deg (as shown in Table 1 and Fig. 3 c). Although these solution-based experiments do not perfectly mimic the polaronic degradation in the emissive layers, they underscore the notably lesser stability of the MR-TADF compounds' radical cations compared to their excitons. Moreover, an inverse correlation was observed between LT 95 and the Faradaic yield (see Fig. 3 d). While not definitive, this negative linear relationship implies a close association between the positive polarons of MR-TADF molecules and the operational stability of OLEDs. The observed relationship between the operational stability of OLEDs and the stability of MR-TADF molecules is further supported by examining the behavior of trapped hole carriers within these dopants. The ideality factor [( k B T / q )⋅(∂ln J /∂ V )] −1 for devices using compounds 1−4 consistently exceeds two, as shown in Supplementary Fig. 8, where k B is the Boltzmann constant, T is the absolute temperature, q is the elementary charge, J is the current density, and V is the voltage. This finding suggests significant charge carrier trapping within the MR-TADF molecules. 34 In single carrier devices designed for exclusive hole transport, the hole current density profiles vary according to the specific MR-TADF dopant used, as depicted in Supplementary Fig. 9. The sequence of hole trapping within the dopants is observed to follow the order 2 > 4 ~ 3 > 1 . This order, conjunction with the Faradaic yield data, offers a coherent kinetic rationale for the observed LT 95 values of the OLED devices. This rationale is predicated on the assumption that the degradation rate adheres to pseudo first-order kinetics, with the rate equation modeled as rate = k ⋅[ D •+ ] = exp(− E a / k B T )⋅[ D •+ ], where k is the rate constant for degradation, [ D •+ ] is the molar concentration of the radical cation of an MR-TADF dopant, and E a is the activation energy for the rate-determining step. Under this framework, the device utilizing compound 1 exhibits the longest LT 95 , attributable to molecule 1 having the smallest Faradaic yield, indicative of the highest intrinsic stability, and the lowest density of positive polarons, leading to the lowest concentration of the degradation intermediates. Conversely, the notably shorter LT 95 for the device incorporating compound 4 can be explained by its high Faradaic yield and dense population of positive polarons, highlighting a direct correlation between these factors and device longevity. Degradation mechanism To shed light on the degradation mechanism of MR-TADF materials, we analyzed a byproduct formed from radical cations. Electrospray ionization (ESI) mass spectrometry in positive mode revealed a significant peak at an m / z value of 810.51 amu in an electrolyzed solution of compound 4 , as shown in Fig. 4 a. This peak corresponds to a species involving [ 4 − 2H], precisely matching with the theoretical isotope distribution. Notably, the pristine sample of 4 lacks this peak, underscoring that the cyclization product specifically arises from the radical cation state. This structural assignment gains additional support from the appearance of new peaks in the 1 H NMR (300 MHz, CD 2 Cl 2 ) spectrum, indicative of a non-symmetric aromatic framework formation, as depicted in Fig. 4 b. An independently synthesized non-symmetric cyclization compound (labeled as compound 4′ , see Fig. 4 b) shows 1 H NMR peaks corresponding to those observed in the oxidation byproduct. This observation aligns with known electrochemical intramolecular C − C coupling reactions among radical cations of various arylamines. 35,36 Further evidence for the intermediacy of the radical cation in the cyclization reaction comes from spectroelectrochemical measurements. Upon applying an anodic potential of 1.04 V versus a saturated calomel electrode (SCE) to an argon-saturated THF solution containing 10 µM of compound 4 and 0.10 M tetrabutylammonium hexafluorophosphate as supporting electrolyte, a broad absorption band appears in the 500 − 700 nm region (Fig. 4 c). This absorption signature is replicated upon the electrochemical oxidation of 4 with [FeCl 3 ] as a strong oxidant (Fig. 4 d), signifying that the visible absorption band originates from the radical cation of a cyclized compound. This is corroborated by the identical absorption band observed upon the electrochemical oxidation of compound 4′ at a potential of 0.18 V vs Ag +/0 (Fig. 4 e). Collectively, our experimental findings converge on the oxidative cyclization as a pivotal degradation pathway of the MR-TADF molecule. Quantum chemical calculations on the oxidative degradation of compounds 1 – 4 suggest heterobimolecular hydrogen atom abstraction, followed by cyclization, as the most likely degradation pathway, in good agreement with experimental evidence. Initial exploration into unimolecular reactions, where bond cleavage might lead to degradation, showed that the C–C single bonds in the neutral dopant molecule strengthen upon oxidation. This is due to the antibonding character of the HOMO in the neutral compound between π-conjugated fragments, which increases bond order upon one-electron oxidation (Supplementary Table 1). Consequently, unimolecular processes are unlikely to be the primary degradation pathways for these emitter molecules. Subsequent investigation into bimolecular reactions identified intermolecular hydrogen atom transfer (HAT) as a key step, initiated by electrogenerated radical species. 37 The reaction free energies for HAT, detailed in Table 3 , reveal that hydrogen atom abstraction from the radical cation of the MR-TADF compound (reaction a ) is energetically favorable, with free energy values between 4.9 and 7.8 kcal mol −1 . This contrasts with hydrogen atom addition to the radical cation (reaction b ), which is less favorable, exhibiting energies between 8.9 and 15.6 kcal mol −1 . The favored reaction leads to the formation of a fused five-membered ring via the C–C bond formation, ortho to the nitrogen atom. This process, culminating in extended π-conjugation within the cyclized product, significantly contributes to its energetic stabilization, thereby rendering the reaction irreversible and highlighting oxidative cyclization as a pivotal degradation mechanism in MR-TADF materials. Table 3. Free energy change for hydrogen atom transfer reactions of the radical cation of MR-TADF dopants a a Energies in kcal mol − 1 , calculated at B3LYP-D3/Def2-TZVP//B3LYP-D3/Def2-SVP level of theory. The kinetic aspect of the hydrogen atom abstraction in the degradation of MR-TADF dopants was investigated by locating the key transition states on the potential energy surface. As illustrated in Fig. 5 , we conceptualize the reaction as a sequential process, delineating the intermolecular HAT followed by the subsequent intramolecular cyclization. Initially, the radical cation of the hole-transporting host ( Host •+ ) abstracts a hydrogen atom of the radical cation of the dopants ( D •+ ), forming an open-shell intermediate [D − H] + os . This initial step is energetically demanding, primarily because the unpaired electron in [D – H] + os is localized on a carbon atom. However, the subsequent cyclization step provides the necessary thermodynamic driving force, spreading the spin density across the molecule through π-conjugation and leading to a stable structure. The cyclization phase reaches a critical point at the transition state ( TS ), identified by the formation of a new C–C bond. Our analysis reveals a consistent energetic cost for the initial HAT across compounds 1 – 4 , averaging around 57 kcal mol −1 , as enumerated in Table 4 , indicating that the variance in dopant reactivity does not stem from the energy required to cleave the C–H bond. Instead, it is the activation energies for the cyclization that determines the differences in dopant reactivity. The step barrier of the cyclization (ΔG ‡ cyc ), representing the energy ascent to reach TS from the intermediate [D – H] + os , varies among the dopants, being highest for 2 (8.2 kcal mol − 1 ), followed by 1 and 3 (6.4 and 6.1 kcal mol − 1 ), and lowest for 4 (4.9 kcal mol − 1 ). This pattern suggests that the extent of π-conjugation achieved through cyclization significantly influences reactivity, with compound 4 , possessing the smallest π-system, achieving the greatest stabilization post-cyclization, in contrast to compound 2 , which has a larger π-cloud and thus gains less energy from cyclization. The spin density distributions before and after cyclization are illustrated in Supplementary Fig. 10. Table 4 Energy components of the hydrogen atom abstraction of MR-TADF dopants 1–4. a energy (kcal mol − 1 ) 1 2 3 4 Δ G HAT 57.21 57.48 57.28 56.88 Δ G ‡ cyc 6.36 8.17 6.08 4.91 a Energies calculated at B3LYP-D3/Def2-TZVP//B3LYP-D3/Def2-SVP level of theory. This kinetic analysis, coupled with the previously discussed charge carrier trapping within the dopants, elucidates the observed stability trends. Despite compound 2 having the highest hole concentration, its better-than-expected stability compared to compounds 3 and 4 can be attributed to its relatively large cyclization energy barrier. Between compounds 3 and 4 , both having similar hole concentrations, the compound 4 's lower stability is ascribed to its higher intrinsic reactivity due to a lower cyclization barrier. This comprehensive kinetic perspective reveals the nuanced interplay between structural features, electronic properties, and degradation pathways, offering a deeper understanding of MR-TADF dopant stability. Finally, we investigated the deleterious effect of the degradation byproduct on the operational stability of devices. The photoluminescence spectrum of compound 4′ shows a minor bathochromic shift of 30 nm compared to that of 4 , as depicted in Supplementary Fig. 11. Contrary to initial assumptions, the robust emission from compound 4′ disputes the notion that it would impair device performance by quenching excitons or acting as a nonradiative charge carrier recombination center. This is further supported by the unaltered electroluminescence spectra between pristine devices and those operated up to the LT 80 and LT 50 benchmarks for compounds 1 − 4 , represented in Supplementary Fig. 12. Such consistency in emission profiles suggests that the luminescent pathways of compound 4′ do not contribute to device deterioration. However, a notable gradual decrease in current density was observed over operational time, indicating poor current performance in devices incorporating compounds 1 − 4 when assessed at their respective LT 80 and LT 50 durations (Supplementary Fig. 13). This decline in current levels correspondingly led to diminished luminance, power efficiency, and EQE , as detailed in Supplementary Table 3 and Fig. 14 − 16. These findings collectively hint at the formation of charge carrier traps within the cyclized byproducts of MR-TADF dopants, a theory further supported by the steady increase in operational voltage over time (Supplementary Fig. 17). In fact, 4′ has the HOMO shallower than that of 4 , supporting this notion (Supplementary Fig. 4). Although we are cautious to draw direct proportionalities, we find rough correlations between the voltage rise and the LT 95 values and the Faradaic yield values (Supplementary Fig. 18). Deuteration effect Deuteration has recently been demonstrated to be a viable strategy for improving the operational stability of hosts, 38–41 and phosphorescent 42–45 and dipolar TADF emitters. 46,47 However, the specific mechanism by which deuterium confers protective benefits to OLED materials has not been fully elucidated. Our study suggests that the enhanced stability results from the substitution of C − H bonds with C − D bonds within the radical cation, considering our degradation mechanism centers on heterobimolecular HAT via homolytic cleavage of the C − H bond. To test this hypothesis and validate our proposed mechanism, we compared the intrinsic stability of a deuterated version of compound 1 , denoted as 1D , with its protiated form, utilizing oxidative bulk electrolysis techniques. Compound 1 , chosen for its superior polaronic stability as indicated by its Faradaic yield, served as a model for this investigation. Our results unambiguously demonstrate the enhanced longevity of 1D , with its oxidative degradation Faradaic yield being 30%, approximately 7% lower than that of compound 1 (Fig. 6 a and b). This finding aligns with our quantum chemical calculations, reinforcing the premise that intermolecular hydrogen atom abstraction constitutes the primary degradation pathway. Further comparative studies were conducted on multilayer OLEDs fabricated with the identical configuration as used previously, substituting 1 with 1D . The key electroluminescence data are compiled in Supplementary Table 4. Unsurprisingly, the electroluminescence spectrum and the current density versus voltage profiles of the device incorporating 1D closely mirrored those of the device based on compound 1 . Notably, a modest increase in the EQE was observed for the 1D -based device (24.0%) compared to the 1 -based device (23.1%) at a current density of 0.01 mA cm −2 , while their roll-off profiles remained virtually identical (Fig. 6 e). Moreover, the operational lifetime experienced a notable improvement with the inclusion of 1D , with the LT 95 reaching approximately 4.3 hours, an increase of about 20% over the LT 95 of the device based on compound 1 (Fig. 6 f). This analysis underscores the critical role of deuteration in mitigating degradation pathways through altering the dynamics of hydrogen atom abstraction, thus offering strong support for the proposed degradation mechanism. Discussion Organic molecules that exhibit MR-TADF have become vital to the development of highly efficient OLEDs with saturated color purity. Despite their significance, research that closely examines the relationship between the operational lifetimes of OLEDs and the intrinsic stability of MR-TADF compounds is notably rare, even though the device longevity is crucial for commercial viability. In our study, we discovered that the operational lifetime of OLEDs is not directly linked to the excitonic stability of MR-TADF molecules 1 − 4 . Instead, our investigations, particularly through bulk electrolysis experiments, highlighted the pronounced instability of the one-electron oxidized forms of these molecules. We established a clear correlation between the Faradaic yield for oxidative degradation and the operational lifetime of the devices, identifying radical cations—or positive polarons—as the critical intermediates that dictate device longevity. Chemical analyses, encompassing mass spectrometry, 1 H NMR spectroscopy, and UV − Vis spectroelectrochemical measurements, have demonstrated the formation of a cyclization byproduct following hole trapping in the MR-TADF compounds. This conclusion is further supported by our independent synthesis of the cyclization byproduct (compound 4′ ). Quantum chemical calculations suggested that oxidative cyclization is the primary degradation pathway for the oxidized dopants. This process begins with hydrogen atom abstraction by another radical cation, specifically targeting the C–H bond ortho to the nitrogen atom on the N -aryl substituent. Subsequent intramolecular cyclization, driven by the need to achieve extended π-conjugation, leads to the irreversible C–C bond formation. Our findings offer a strategic approach to enhancing the stability of MR-TADF molecules for OLED applications: by reinforcing the C − H bond at electrochemically active sites, such as the ortho - and para -positions relative to nitrogen atoms in the azaborine unit. This approach was empirically validated through the synthesis of a deuterated MR-TADF compound ( 1D ), which not only demonstrated a reduced Faradaic yield for oxidative degradation but also significantly extended the operational lifetime compared to its undeuterated counterpart. This research underscores the importance of managing electrochemical reactivity to ensure the high stability of MR-TADF molecules. Given the extensive body of existing research on the electrochemical behaviors of arylamine-based organic molecules, 48 we anticipate that the insights gained from our study, combined with existing knowledge, will pave the way for the design and development of highly stable MR-TADF molecules for electroluminescence applications. Methods General procedures. Chemicals were purchased from commercial suppliers, and used without further purification. 1 H and 13 C{ 1 H} NMR spectra were recorded on a Bruker AVANCE III HD 500 spectrometer and a Bruker AVANCE III 600 spectrometer, with CD 2 Cl 2 as the solvent. Chemical shifts were referenced to the peaks corresponding to residual solvents. We examined the purity and mass spectra of materials by performing liquid chromatography mass spectrometer-ion trap-time of flight (LCMS-IT-TOF) analyses. The LCMS-IT-TOF instrumentation consisted of a Shimadzu LC-30A Nexera SR System instrument connected to a hybrid IT-TOF mass spectrometer equipped with an ESI source. Compound 2 was prepared following the method of Kondo et al . 10 Compound 4 was prepared following the method of Han et al . 31 Organic materials for device fabrication were purchased from commercial suppliers and were purified by sublimation at 10 − 5 torr prior to deposition. PMMA (Mw ~ 120,000, Sigma−Aldrich) films doped with the MR-TADF dopants (2 wt %) were dissolved in 1,2-dichoroethane (5 wt % total solute relative to solution). The solution was sonicated for 30 min, and passed through a membrane filter (pore size = 8.0 µm). An aliquot of the polymer solution was placed on a pre-cleaned glass substrate and was spin-cast using an EPLEX, SPIN-1200D spin coater. Spectrophotometric-grade THF stored under an inert atmosphere was used for spectroscopic and electrochemical measurements. Synthesis of 1. A tert -butyllithium solution (1.7 M in pentane, 8.50 mL, 14.5 mmol) was added dropwise to a stirred solution of N 1 , N 1 , N 3 , N 3 -tetra([1,1'-biphenyl]-4-yl)-2-chlorobenzene-1,3-diamine (5.19 g, 6.90 mmol) in tert -butylbenzene (70 mL) at 0 ℃ under a N 2 atmosphere. The resulting mixture was heated to 60 ℃ and stirred for an hour. The solution was cooled to −78 ℃, and boron tribromide (1.40 mL, 14.5 mmol) was slowly added. The resultant mixture was stirred for 2 h at 0 ℃. After additional stirring, diisopropylethylamine (2.40 mL, 13.8 mmol) was added to the reaction mixture at 0 ℃ and then the reaction mixture was heated to 110 ℃ and stirred for 3 h. The resultant mixture was cooled to 0 ℃ and then carefully quenched with saturated aq. NaHCO 3 solution. Extraction was performed with dichloromethane; the collected organic layer was dried over MgSO 4 , filtered, and concentrated in vacuo . The crude mixture was purified by column chromatography on silica gel. The obtained product was recrystallized from dichloromethane/hexane/methanol to give 1 as a yellow solid (2.24 g, 45%). 1 H NMR (500 MHz, CD 2 Cl 2 ): δ 9.39 (d, J = 2.0 Hz, 2H), 7.97 (d, J = 8.5 Hz, 4H), 7.84 (d, J = 8.0 Hz, 4H), 7.77 (d, J = 8.0 Hz, 6H), 7.48−7.55 (m, 12H), 7.44 (t, J = 8.0 Hz, 2H), 7.36 (t, J = 7.5 Hz, 2H), 7.34 (t, J = 8.5 Hz, 1H), 7.00 (d, J = 9.0 Hz, 2H), 6.32 (d, J = 8.0 Hz, 2H). 13 C{ 1 H} NMR (125 MHz, CD 2 Cl 2 ): δ 147.16, 146.83, 141.62, 141.29, 141.16, 140.13, 133.32, 132.37, 132.22, 130.73, 129.80, 128.91, 127.83, 127.20, 126.77, 126.73, 117.75, 105.60. MS (ESI): m / z calculated for C 54 H 38 BN 2 [M + H] + : 725.312, Found: 725.302. Synthesis of 3. The full synthetic details are described in Supplementary Method 1. A tert -butyllithium solution (1.7 M in pentane, 8.50 mL, 14.5 mmol) was added dropsie to a stirred solution of N 5 -([1,1'-biphenyl]-2-yl)- N 1 , N 1 , N 3 , N 3 , N 5 -penta([1,1'-biphenyl]-4-yl)-2-chlorobenzene-1,3,5-triamine (6.19 g, 5.78 mmol) in tert -butylbenzene (100 mL) at 0 ℃ under an N 2 atmosphere. The resultant mixture was heated to 60 ℃ and stirred for 2 h. The solution was then cooled to −78 ℃, and boron tribromide (1.40 mL, 14.5 mmol) was slowly added. The resultant mixture was stirred for an hour at 0 ℃. After additional stirring, diisopropylethylamine (2.50 mL, 14.3 mmol) was added to the reaction mixture at 0 ℃, then the reaction mixture was heated to 110 ℃ and stirred for 3 h before being cooled to 0 ℃ and carefully quenched with saturated aq. NaHCO 3 solution. The crude product was then extracted with dichloromethane, and the collected organic layer was dried over MgSO 4 , filtered, and concentrated in vacuo . The crude mixture was purified by column chromatography on silica gel. Then the obtained product was suspended to ethyl acetate. The suspension was heated to 80 ℃ and stirred for an hour. The insoluble solid was collected by filtration to give 3 as a yellow solid (1.8 g, 30%). 1 H NMR (600 MHz, CD 2 Cl 2 ): δ 9.33 (d, J = 2.4 Hz, 2H), 7.82 (d, J = 8.4 Hz, 4H), 7.75 (d, J = 8.4 Hz, 4H), 7.71 (dd, J = 9.0 Hz, 2.4 Hz, 2H), 7.56 (d, J = 6.6 Hz, 4H), 7.50 (t, J = 8.0 Hz, 4H), 7.33–7.42 (m, 11H), 7.27–7.31 (m, 5H), 7.21–7.24 (m, 1H), 7.14–7.16 (m, 4H), 7.11–7.14 (m, 1H), 7.04–7.08 (m, 4H), 6.99 (dd, J = 7.8 Hz, 2H), 6.97 (d, J = 8.4 Hz, 2H), 6.79 (d, J = 8.4 Hz, 2H), 5.63 (s, 2H). MS (ESI): m / z calculated for C 78 H 55 BN 3 [M + H] + : 1044.448, Found: 1044.452. Synthesis of 1D. The full synthetic details are described in Supplementary Method 2. A tert -butyllithium solution (1.7 M in pentane, 5.50 mL, 9.35 mmol) was added dropwise to a stirred solution of N 1 , N 1 , N 3 , N 3 -tetrakis([1,1'-biphenyl]-4-yl- d 9 )-2-chlorobenzene-1,3-diamine (3.50 g, 4.45 mmol) in tert -butylbenzene (90 mL) at 0 ℃ under an N 2 atmosphere. The resultant mixture was heated to 60 ℃ and stirred for an hour. The solution was cooled to −78 ℃ and boron tribromide (0.90 mL, 9.34 mmol) was slowly added. The resultant mixture was stirred for 2 h at 0 ℃. After additional stirring, diisopropylethylamine (1.60 mL, 9.15 mmol) was added to the reaction mixture at 0 ℃; the mixture was then heated to 110 ℃ and stirred for 3 h. The resultant mixture was cooled to 0 ℃ and carefully quenched with saturated aq. NaHCO 3 solution. The crude product was then extracted with dichloromethane, and the collected organic layer was dried over MgSO 4 , filtered, and concentrated in vacuo . The crude mixture was purified by column chromatography on silica gel. Then the obtained product was recrystallized from dichloromethane/hexane/methanol to give 1D as a yellow solid (0.800 g, 24%). 1 H NMR (500 MHz, CD 2 Cl 2 ): δ 7.98 (s, 0.17H), 7.84 (s, 2.1H), 7.78 (s, 2.3H), 7.51–7.55 (m, 1H), 7.44 (s, 0.3H), 7.37 (s, 0.28H), 7.35 (t, J = 8.5 Hz, 1H), 6.99 (s, 0.4H), 6.32 (d, J = 8.5 Hz, 2H); deuterium is incorporated at ~ 80%. 13 C{ 1 H} NMR (125 MHz, CD 2 Cl 2 ): δ 147.11, 146.84, 141.17, 132.21, 127.07, 126.62, 105.56. MS (ESI): m / z calculated for C 54 H 10 D 27 BN 2 [M-7D + 7H] + : 751.474, Found: 751.387. Device fabrication and characterization. The organic layers were deposited consecutively onto pre-cleaned ITO glass substrates using a thermal evaporation system at a pressure less than 1.0 × 10 −6 torr. A 1 nm-thick LiQ layer and a 100 nm-thick Al layer were deposited as a cathode via thermal evaporation. The deposition rates of the organic and metal layers were 0.1 nm s −1 and 0.5 nm s −1 , respectively. LiQ was deposited at a rate 0.01 nm s −1 . The active device area of 4 mm 2 was defined by the area of overlap between the ITO and Al electrodes. The current, voltage, and luminance of the OLED devices were measured with a system comprising a Keithley 2400 Source-Meter and a Topcon SR-3AR spectroradiometer. Operational lifetime measurements of the devices were conducted in a constant-current mode. Current−voltage characteristics of single-carrier devices with the device structure introduced in Supplementary Fig. 9 were measured with a system consisting of a Keithley 2400 source-meter. On the basis of the lack of emission under the given voltage, we inferred that only hole transport occurred within the single-carrier devices. Steady-state UV−Vis absorption measurements . UV−Vis absorption spectra were collected at 298 K using an Agilent Cary 300 spectrophotometer. Stock solutions with a concentration of 10 mM were prepared in THF. Sample solutions with a concentration of 10 µM in THF, which had been previously saturated with Ar, were prepared prior to the measurements by diluting the stock solution, unless otherwise stated. A total of 3.0 mL of each solution was added to a quartz cell (Hellma, beam path length = 1.0 cm). Steady-state photoluminescence measurements . Photoluminescence spectra were obtained at 298 K by using a Photon Technology International Quanta Master 400 scanning spectrofluorometer. Samples for the measurements were prepared as 10 µM solutions in THF, unless otherwise stated. The solutions were deaerated by bubbling Ar gas for at least 10 min before the measurement. All operations were controlled with the FelixGX software provided by the manufacturer. Photoluminescence lifetime measurements . PMMA films doped with (quartz substrate) 2 wt % 1−4 were used for the determination of the photoluminescence lifetimes. Photoluminescence decay traces were acquired using time-correlated single-photon-counting techniques with a PicoQuant, FluoTime 200 instrument after picosecond pulsed laser excitation (pulse duration = 2.5 ns). A diode laser that produced 377 nm pulses (PicoQuant, LDH375) was driven by a PDL800-D driver (PicoQuant). Transient photon signals were collected at λ obs = 471 nm ( 1 ), 467 nm ( 2 ), 461 nm ( 3 ), and 459 nm ( 4 ). The burst mode was used to monitor delayed fluorescence. The fluorescence signals at the emission peak wavelengths of the compounds were obtained with an automated motorized monochromator. Photoluminescence decay profiles were analyzed (OriginPro 8.0, OriginLab) using a biexponential decay model. Temperature-dependent measurements were conducted in the temperature range 79−315 K using an Oxford Instruments Omicron Nanoscience, Optistat DN2 variable-temperature liquid N 2 cryostat equipped with a MercuryiTC temperature controller. Electrochemical characterization . Cyclic and differential pulse voltammetry experiments were conducted using a CH Instruments CHI630 B potentiostat in conjunction with a three-electrode cell assembly. A Pt wire and a glassy carbon disc were used as the counter and working electrodes, respectively. A Ag/AgNO 3 couple was used as the pseudo-reference electrode. Measurements were carried out in Ar-saturated THF (2.0 mL) with 0.10 M tetrabutylammonium hexafluorophosphate as the supporting electrolyte at scan rates of 100 mV s −1 (cyclic voltammetry) and 4.0 mV s −1 (differential pulse voltammetry). The ferrocenium/ferrocene couple was used as an external reference. Spectroelectrochemical measurements . UV−Vis absorption spectra of the radical species were acquired via the amperometric I − t curve method using an Agilent Cary 300 spectrophotometer with anodic potentials applied. A blank spectrum was acquired for a 0.10 M tetrabutylammonium hexafluorophosphate solution (THF) in a spectroelectrochemical cell (path length = 0.5 mm) equipped with a Pt mesh working electrode, a Pt wire counter electrode, and a Ag/AgNO 3 pseudo reference electrode. A 1.0 mM sample solution (500 µL) was delivered into the spectroelectrochemical cell for the measurement. Photolysis. An Ar-saturated 25 mL THF solution containing 100 µM sample was placed in a 40 mL scintillation vial equipped with a Teflon-coated magnetic stir bar. The solution was photoirradiated using a monochromatic light source (450 nm) positioned 1 cm from the vial. Aliquots of the 100 µL reaction mixture were collected during the photolysis reaction and diluted with 50 µL of 1.0 mM of benzophenone in THF and 850 µL CH 3 CN for quantification of the residual concentration of the components. High-performance liquid chromatography (HPLC) experiments were performed on an Agilent 6120 DW LC/MSD instrument equipped with a Poroshell, EC-C18 column. The photolyzed solutions, diluted in HPLC grade CH 3 CN (1:4, v/v), were passed through a poly(vinylidene fluoride) (PVDF) membrane filter (pore size = 8.0 µm) prior to injection. A 5 µL sample volume was injected and allowed to pass through the column at room temperature; a gradient eluent with increasing fractions of CH 3 CN in H 2 O was used. The quantum yields for photolysis ( Φ deg ) were determined according to Eq. 1: $${\varPhi }_{\text{d}\text{e}\text{g}}=\frac{{k}_{\text{o}\text{b}\text{s}}\times V}{\left(1-{10}^{-Abs}\right)\times q} \left(\text{e}\text{q} 1\right)$$ ,where k obs represents the degradation rate corresponding to the slope of the linear fit of the initial five data points shown in Supplementary Fig. 6b, V is the volume of the solution (25 mL), 1 − 10 − Abs is the photokinetic factor based on the absorbance at a wavelength of 450 nm, and q is the photon flux (4.0 × 10 −8 einstein s −1 ) determined using standard ferrioxalate actinometry and additionally confirmed using an optical powermeter. Oxidative bulk electrolysis. Oxidative bulk electrolysis experiments were conducted using 25 mL of Ar-saturated THF solutions containing 200 µM sample, along with 0.10 M tetrabutylammonium hexafluorophosphate, in a 40 mL scintillation vial equipped with a Teflon-coated magnetic stir bar. Oxidative bulk electrolysis was performed at potentials of 1.04 V vs SCE for 1 and 3 , 1.01 V vs SCE for 2 , and 0.98 V vs SCE for 4 . A Pt mesh and a Pt coil served as the working and counter electrodes, respectively. A Ag/AgNO 3 pseudo-reference electrode was used. Changes in the Faradaic charge transferred from the working electrode during oxidative bulk electrolysis were monitored. Aliquots of the 100 µL reaction mixture were collected during the electrolysis reaction and diluted with 50 µL of 1.0 mM benzophenone in THF and 850 µL CH 3 CN for quantification of the residual concentration of the components. HPLC experiments were performed on an Agilent 6120 DW LC/MSD instrument equipped with a Poroshell, EC-C18 column. The electrolyzed solutions, diluted in HPLC grade CH 3 CN (1:4, v/v), were passed through a PVDF membrane filter (pore size = 8.0 µm) prior to injection. A 5 µL sample volume was injected and allowed to pass through the column at room temperature; a gradient eluent with increasing fractions of CH 3 CN in H 2 O was used. The Faradaic yield for oxidative bulk electrolysis was determined following Eq. 2: $$\text{F}\text{a}\text{r}\text{a}\text{d}\text{a}\text{i}\text{c} \text{y}\text{i}\text{e}\text{l}\text{d}=\frac{{k}_{\text{o}\text{b}\text{s}}\times V\times t}{C\times F} \left(\text{e}\text{q} 2\right)$$ ,where k obs is the degradation rate corresponding to the slope of the linear fit of the initial five data points shown in Fig. 3 b, V is the volume of the solution (25 mL), t is the reaction time, C is the total charge transferred at time t , and F is the Faraday constant. Degradation product analyses. ESI mass analyses were performed under positive-ion detection mode (voltage = 70 V) in the range 200−1500 amu. Calculation methods. All density functional theory (DFT) 49 calculations were performed with the Orca 4.2 suite of quantum chemistry programs. 50 Geometries of intermediates and transition states were optimized with B3LYP 51,52 hybrid functional along with Grimme’s D3 dispersion 53 correction (B3LYP-D3) using the Ahlrichs balanced basis sets of split valence quality, Def2-SVP. 54 The RIJCOSX approximation 55,56 was employed using the Def2/J auxiliary basis set. 57 Single point calculations were carried out with the valence polarized triple-zeta quality Ahlrichs basis set, Def2-TZVP, 54 to obtain more reliable electronic energies. To evaluate the zero-point energy (ZPE) and entropy correction, the frequency calculations were performed at the same level of theory used in the geometry optimization. Because the dopant and HT host molecules are confined in the device in the solid phase, solvation correction was not included in evaluating the Gibbs free energies. Declarations Data availability The data that support the findings of this study are available from the corresponding author upon reasonable request. Acknowledgements This work was supported by the Midcareer Research Program (RS-2023-00208856) through National Research Foundation grants funded by the Ministry of Science, Information, and Communication Technology (ICT) and Future Planning (MSIP), and by the Institute for Basic Science in Korea (IBS-R010-A1). Author Contributions B.H.J. performed the spectroscopic experiments, analyzed the data, and wrote the manuscript. H.S.K. synthesized and characterized the materials, and co-wrote the manuscript. J.K. fabricated and tested the devices. Y.P., E.L., H.M., and C.J. conducted and analyzed the quantum chemical calculations and Y.P. co-wrote the manuscript. Y.J. coordinated the material preparation and OLED experiments. S.C. performed the electrochemical experiments. M.-H.B. supervised the quantum chemical calculations at KAIST, and co-wrote the manuscript. Y.Y. coordinated all of the experiments and analyses, and co-wrote the manuscript. All authors contributed to discussion on the study, and edited the manuscript. Additional information Supplementary information is available in the online version of the paper. Reprints and permissions information are available online at www.nature.com/reprints . Correspondence and requests for materials should be addressed to Y.Y. ( [email protected] ). Competing interests The authors declare no competing interests. References Baranoff, E., Yum, J.-H., Graetzel, M. & Nazeeruddin, M. K. Cyclometallated iridium complexes for conversion of light into electricity and electricity into light. J. Organomet. Chem. 694 , 2661-2670 (2009). Longhi, E. & De Cola, L. in Iridium (III) in Optoelectronic and Photonics Applications (ed Eli Zysman-Colman) 205-274 (John Wiley & Sons Ltd., 2017). Kalinowski, J., Fattori, V., Cocchi, M. & Williams, J. A. G. Light-emitting devices based on organometallic platinum complexes as emitters. Coord. Chem. Rev. 255 , 2401-2425 (2011). Tang, M.-C., Chan, A. K.-W., Chan, M.-Y. & Yam, V. W.-W. Platinum and gold complexes for OLEDs. Top. Curr. Chem. 374 , 46 (2016). Liu, Y., Li, C., Ren, Z., Yan, S. & Bryce, M. R. All-organic thermally activated delayed fluorescence materials for organic light-emitting diodes. Nat. Rev. Mater. 3 , 18020 (2018). Shizu, K. et al. Highly efficient electroluminescence from purely organic donor-acceptor systems. Pure Appl. Chem. 87 , 627-638 (2015). Czerwieniec, R., Leitl, M. J., Homeier, H. H. H. & Yersin, H. Cu(I) complexes-Thermally activated delayed fluorescence. Photophysical approach and material design. Coord. Chem. Rev. 325 , 2-28 (2016). Osawa, M. et al. Application of neutral d 10 coinage metal complexes with an anionic bidentate ligand in delayed fluorescence-type organic light-emitting diodes. J. Mater. Chem. C 1 , 4375-4383 (2013). Hatakeyama, T. et al. Ultrapure blue thermally activated delayed fluorescence molecules: efficient HOMO–LUMO separation by the multiple resonance effect. Adv. Mater. 28 , 2777–2781 (2016). Kondo, Y. et al. Narrowband deep-blue organic light-emitting diode featuring an organoboron-based emitter. Nat. Photonics 13 , 678–682 (2019). Pershin, A. et al. Highly emissive excitons with reduced exchange energy in thermally activated delayed fluorescent molecules. Nat. Commun. 10 , 597 (2019). Naveen, K. R., Palanisamy, P., Chae, M. Y. & Kwon, J. H. Multiresonant TADF materials: triggering the reverse intersystem crossing to alleviate the efficiency roll-off in OLEDs. Chem. Commun. 59 , 3685-3702 (2023). Suresh, S. M., Hall, D., Beljonne, D., Olivier, Y. & Zysman-Colman, E. Multiresonant thermally activated delayed fluorescence emitters based on heteroatom-doped nanographenes: recent advances and prospects for organic light-emitting diodes. Adv. Funct. Mater. 30 , 1908677 (2020). Ha, J. M., Hur, S. H., Pathak, A., Jeong, J.-E. & Woo, H. Y. Recent advances in organic luminescent materials with narrowband emission. NPG Asia Mater. 13 , 53 (2021). Monkman, A. Why do we still need a stable long lifetime deep blue OLED emitter? ACS Appl. Mater. Interfaces 14 , 20463–20467 (2022). Kim, H. J. & Yasuda, T. Narrowband emissive thermally activated delayed fluorescence materials. Adv. Optical Mater. 10 , 2201714 (2022). Fan, X. et al. RGB thermally activated delayed fluorescence emitters for organic light-emitting diodes toward realizing the BT.2020 standard. Adv. Sci. 10 , 2303504 (2023). Aziz, H. & Popovic, Z. D. Degradation phenomena in small-molecule organic light-emitting devices. Chem. Mater. 16 , 4522-4532 (2004). So, F. & Kondakov, D. Degradation mechanisms in small-molecule and polymer organic light-emitting diodes. Adv. Mater. 22 , 3762-3777 (2010). Schmidbauer, S., Hohenleutner, A. & König, B. Chemical degradation in organic light-emitting devices: mechanisms and implications for the design of new materials. Adv. Mater. 25 , 2114-2129 (2013). Scholz, S., Kondakov, D., Luessem, B. & Leo, K. Degradation mechanisms and reactions in organic light-emitting devices. Chem. Rev. 115 , 8449-8503 (2015). Jeon, S. K., Lee, H. L., Yook, K. S. & Lee, J. Y. Recent progress of the lifetime of organic light‐emitting diodes based on thermally activated delayed fluorescent material. Adv. Mater. 31 , 1803524 (2019). Kim, S. et al. Degradation of blue-phosphorescent organic light-emitting devices involves exciton-induced generation of polaron pair within emitting layers. Nat. Commun. 9 , 1211 (2018). Moon, Y. K. et al. Modeling Electron-Transfer Degradation of Organic Light-Emitting Devices. Adv. Mater. 33 , 2003832 (2021). Zhao, C., Li, C., Li, Y., Qiu, Y. & Duan, L. Understanding the operational lifetime expansion methods of thermally activated delayed fluorescence sensitized OLEDs: a combined study of charge trapping and exciton dynamics. Mater. Chem. Front. 3 , 1181-1191 (2019). Lee, Y.-T. et al. Tailor-Made Multi-Resonance Terminal Emitters toward Narrowband, High-Efficiency, and Stable Hyperfluorescence Organic Light-Emitting Diodes. Adv. Optical Mater. 10 , 2200682 (2022). Meng, G. et al. Highly efficient and stable deep-blue OLEDs based on narrowband emitters featuring an orthogonal spiro-configured indolo[3,2,1- de ]acridine structure. Chem. Sci. 13 , 5622-5630 (2022). Xue, W. et al. Identifying the Molecular Origins of Green BN-TADF Material Degradation and Device Stability via in situ Raman Spectroscopy. Chem. Eur. J. 28 , e202201006 (2022). Wang, X. et al. Improving the stability and color purity of a BT.2020 blue multiresonance emitter by alleviating hydrogen repulsion. Sci. Adv. 9 , eadh1434 (2023). Giebink, N. C. et al. Intrinsic luminance loss in phosphorescent small-molecule organic light emitting devices due to bimolecular annihilation reactions. J. Appl. Phys. 103 , 044509 (2008). Han, S. H., Jeong, J. H., Yoo, J. W. & Lee, J. Y. Ideal blue thermally activated delayed fluorescence emission assisted by a thermally activated delayed fluorescence assistant dopant through a fast reverse intersystem crossing mediated cascade energy transfer process. J. Mater. Chem. C 7 , 3082-3089 (2019). Baldo, M. A., Adachi, C. & Forrest, S. R. Transient analysis of organic electrophosphorescence. II. Transient analysis of triplet-triplet annihilation. Phys. Rev. B 62 , 10967-10977 (2000). Giebink, N. C., D'Andrade, B. W., Weaver, M. S., Brown, J. J. & Forrest, S. R. Direct evidence for degradation of polaron excited states in organic light emitting diodes. J. Appl. Phys. 105 , 124514 (2009). Wetzelaer, G. A. H., Kuik, M., Nicolai, H. T. & Blom, P. W. M. Trap-assisted and Langevin-type recombination in organic light-emitting diodes. Phys. Rev. B 83 , 165204 (2011). Creason, S. C., Wheeler, J. & Nelson, R. F. Electrochemical and spectroscopic studies of cation radicals. I. Coupling rates of 4-substituted triphenylaminium ion. J. Org. Chem. 37 , 4440–4446 (1972). Yurchenko, O. et al. Electrochemically induced reversible and irreversible coupling of triarylamines. J. Phys. Chem. B 116 , 30–39 (2012). Mayer, J. M. Proton-Coupled Electron Transfer: A Reaction Chemist’s View. Annu. Rev. Phys. Chem. 55 , 363–390 (2004). Kondakov, D. Y., Brown, C. T., Pawlik, T. D. & Jarikov, V. V. Chemical reactivity of aromatic hydrocarbons and operational degradation of organic light-emitting diodes. J. Appl. Phys. 107 , 024507 (2010). Liu, X. et al. Isotope effect of host material on device stability of thermally activated delayed fluorescence organic light-emitting diodes. Small Sci. 1 , 2000057 (2021). Tsuji, H., Mitsui, C. & Nakamura, E. The hydrogen/deuterium isotope effect of the host material on the lifetime of organic light-emitting diodes. Chem. Commun. 50 , 14870-14872 (2014). Yao, J., Dong, S.-C., Tam, B. S. T. & Tang, C. W. Lifetime enhancement and degradation study of blue OLEDs using deuterated materials. ACS Appl. Mater. Interfaces 15 , 7255–7262 (2023). Abe, T., Miyazawa, A., Konno, H. & Kawanishi, Y. Deuteration isotope effect on nonradiative transition of fac -tris (2-phenylpyridinato) iridium (III) complexes. Chem. Phys. Lett. 491 , 199-202 (2010). Wang, P. et al. Synthesis of all-deuterated tris(2-phenylpyridine)iridium for highly stable electrophosphorescence: the “deuterium effect”. J. Mater. Chem. C 1 , 4821-4825 (2013). Bae, H. J. et al. Protecting benzylic C-H bonds by deuteration doubles the operational lifetime of deep-blue Ir-phenylimidazole dopants in phosphorescent OLEDs. Adv. Optical Mater. 9 , 2100630 (2021). Li, W. et al. Improved efficiency and stability of red phosphorescent organic light-emitting diodes via selective deuteration. J. Phys. Chem. Lett. 13 , 1494–1499 (2022). Jung, S. et al. Enhancing operational stability of OLEDs based on subatomic modified thermally activated delayed fluorescence compounds. Nat. Commun. 14 , 6481 (2023). Huang, T. et al. Enhancing the efficiency and stability of blue thermally activated delayed fluorescence emitters by perdeuteration. Nat. Photonics (2024). https://doi.org:DOI: 10.1038/s41566-024-01379-1 Karon, K. & Lapkowski, M. Carbazole electrochemistry: a short review. J. Solid State Electrochem. 19 , 2601–2610 (2015). Parr, R. G. & Weitao, Y. Density-Functional Theory of Atoms and Molecules . (Oxford University Press, 1994). Neese, F. Software Update: The ORCA Program System, Version 4.0. Wiley Interdiscip. Rev. Comput. Mol. Sci. 8 , e1327 (2018). Becke, A. D. Density-Functional Exchange-Energy Approximation with Correct Asymptotic Behavior. Phys. Rev. A Gen. Phys. 38 , 3098–3100 (1988). Lee, C., Yang, W. & Parr, R. G. Development of the Colle-Salvetti Correlation-Energy Formula into a Functional of the Electron Density. Phys. Rev. B Condens. Matter 37 , 785–789 (1988). Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A Consistent and Accurate Ab Initio Parametrization of Density Functional Dispersion Correction (DFT-D) for the 94 Elements H-Pu. J. Chem. Phys. 132 , 154104 (2010). Weigend, F. & Ahlrichs, R. Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. Phys. Chem. Chem. Phys. 7 , 3297-3305 (2005). Neese, F. An Improvement of the Resolution of the Identity Approximation for the Formation of the Coulomb Matrix. J. Comput. Chem. 24 , 1740–1747 (2003). Wennmohs, F., Hansen, A. & Becker, U. Efficient, Approximate and Parallel Hartree-Fock and Hybrid DFT Calculations. A “chain-of-Spheres” Algorithm for the Hartree-Fock Exchange. Chem. Phys. 356 , 98–109 (2009). Weigend, F. Accurate Coulomb-Fitting Basis Sets for H to Rn. Phys. Chem. Chem. Phys. 8 , 1057–1065 (2006). Additional Declarations There is NO Competing Interest. Supplementary Files Supplementaryinformation.pdf Supplementary Information Cite Share Download PDF Status: Published Journal Publication published 04 Jan, 2025 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-4184912","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":291880540,"identity":"2d0d0eae-bc75-45f4-8f18-5807fde50fe6","order_by":0,"name":"Youngmin You","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA1klEQVRIiWNgGAWjYFCCBAOGDxUQ5gEQIUGMFsYZZ0jVwszbhsQnqIWfPXnzB955h+XM+Q8fPMBQY8cgOfsAfi2SPc/KJCS3HTa2nJGWcIDhWDKDNF8Cfi0GN3LMGAy3HU7ccIPH4AAD2wEGOR4CDgNqMf6QOAeo5fz5DwcY/hGnxUDiYANQy4EchgOMbQcYpAlpAflFsuFYurHBjTSDA4l9yTySPQS0gELs858aazmD84cff/jwzU5O4gwBLVDQDKESGBgIOQsO6ohVOApGwSgYBSMRAAC1rEWIB2J9WgAAAABJRU5ErkJggg==","orcid":"https://orcid.org/0000-0001-5633-6599","institution":"Yonsei University","correspondingAuthor":true,"prefix":"","firstName":"Youngmin","middleName":"","lastName":"You","suffix":""},{"id":291880541,"identity":"1f76a5fe-c9d9-4d3b-908c-4b1d7705c57c","order_by":1,"name":"Byung Hak Jhun","email":"","orcid":"","institution":"Yonsei University","correspondingAuthor":false,"prefix":"","firstName":"Byung","middleName":"Hak","lastName":"Jhun","suffix":""},{"id":291880542,"identity":"3f53f42d-0031-4835-9c8f-b451c32a95c7","order_by":2,"name":"Hwang Suk Kim","email":"","orcid":"","institution":"Samsung Electronics Co., LTD","correspondingAuthor":false,"prefix":"","firstName":"Hwang","middleName":"Suk","lastName":"Kim","suffix":""},{"id":291880543,"identity":"2f9217bf-4843-4ed0-845c-c3ed73ceef35","order_by":3,"name":"Joonghyuk Kim","email":"","orcid":"https://orcid.org/0009-0000-0119-3359","institution":"Samsung Electronics Co., LTD","correspondingAuthor":false,"prefix":"","firstName":"Joonghyuk","middleName":"","lastName":"Kim","suffix":""},{"id":291880544,"identity":"750f4882-549a-4eab-adbf-d9d205dfcc1d","order_by":4,"name":"Yerin Park","email":"","orcid":"","institution":"Korea Advanced Institute of Science and Technology (KAIST)","correspondingAuthor":false,"prefix":"","firstName":"Yerin","middleName":"","lastName":"Park","suffix":""},{"id":291880545,"identity":"4737623f-2f7a-4a1d-a187-066d8adb6f4b","order_by":5,"name":"Eunji Lee","email":"","orcid":"","institution":"Korea Advanced Institute of Science and Technology (KAIST)","correspondingAuthor":false,"prefix":"","firstName":"Eunji","middleName":"","lastName":"Lee","suffix":""},{"id":291880546,"identity":"9ec4d488-2e54-4bf4-a64a-8dceb89386cd","order_by":6,"name":"Hyejin Moon","email":"","orcid":"","institution":"Korea Advanced Institute of Science and Technology (KAIST)","correspondingAuthor":false,"prefix":"","firstName":"Hyejin","middleName":"","lastName":"Moon","suffix":""},{"id":291880547,"identity":"f47a6a2e-2e50-4d22-b7a6-b31493893fd2","order_by":7,"name":"Changjin Oh","email":"","orcid":"","institution":"Korea Advanced Institute of Science and Technology (KAIST)","correspondingAuthor":false,"prefix":"","firstName":"Changjin","middleName":"","lastName":"Oh","suffix":""},{"id":291880548,"identity":"53d803f6-5b00-4479-b398-166dabf041ee","order_by":8,"name":"Yongsik Jung","email":"","orcid":"https://orcid.org/0000-0003-4496-2351","institution":"Samsung Advanced Institute of Technology","correspondingAuthor":false,"prefix":"","firstName":"Yongsik","middleName":"","lastName":"Jung","suffix":""},{"id":291880549,"identity":"0705c6ab-e33e-41fb-81a5-39faa2d6555c","order_by":9,"name":"Seunghee Choi","email":"","orcid":"","institution":"Ewha Womans University","correspondingAuthor":false,"prefix":"","firstName":"Seunghee","middleName":"","lastName":"Choi","suffix":""},{"id":291880550,"identity":"d01ac84f-c4f4-43e3-8ae1-b85ade59639e","order_by":10,"name":"Mu-Hyun Baik","email":"","orcid":"","institution":"Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS)","correspondingAuthor":false,"prefix":"","firstName":"Mu-Hyun","middleName":"","lastName":"Baik","suffix":""}],"badges":[],"createdAt":"2024-03-29 01:10:13","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4184912/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4184912/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41467-024-55620-0","type":"published","date":"2025-01-04T05:00:00+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":55287026,"identity":"d7735e32-8423-411c-8452-8b26958e9bce","added_by":"auto","created_at":"2024-04-25 08:18:41","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":1672942,"visible":true,"origin":"","legend":"\u003cp\u003eOxidative degradation of MR-TADF dopants. Chemical structures of the MR-TADF dopants and a schematic of the degradation mechanism of an MR-TADF dopant, as established in the present study.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-4184912/v1/51790d5be37782159c66ad7f.png"},{"id":55287354,"identity":"9cc953c9-dff3-4d9b-96e7-306a1cc4e754","added_by":"auto","created_at":"2024-04-25 08:26:41","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":310078,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eElectroluminescence performance.\u003c/strong\u003e \u003cstrong\u003ea,\u003c/strong\u003e Schematic of the configuration of the electroluminescence devices tested, including the energy levels and chemical structures of their component materials. \u003cstrong\u003eb\u003c/strong\u003e, Electroluminescence spectra. \u003cstrong\u003ec\u003c/strong\u003e, Current density–voltage curves. \u003cstrong\u003ed\u003c/strong\u003e, External quantum efficiencies as a function of current density. \u003cstrong\u003ee\u003c/strong\u003e, Percent luminance decays as a function of operation time driven at constant current density at an initial luminance of 1000 cd m\u003csup\u003e-2\u003c/sup\u003e.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-4184912/v1/3b47f725e5c480e043e72f3e.png"},{"id":55287029,"identity":"7cea0113-5dd3-4b45-bb08-e5c1d98b5be5","added_by":"auto","created_at":"2024-04-25 08:18:41","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":298370,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eOxidative degradation.\u003c/strong\u003e \u003cstrong\u003ea,\u003c/strong\u003e Liquid chromatograms of 100 μM \u003cstrong\u003e4\u003c/strong\u003e (Ar-saturated THF containing a 0.10 M tetrabutylammonium hexafluorophosphate supporting electrolyte) obtained during oxidative bulk electrolysis performed at an anodic potential of 1.04 V vs SCE. A Pt mesh and a Pt coil were used for the working and the counter electrodes, respectively. A Ag/AgNO\u003csub\u003e3\u003c/sub\u003e pseudo-reference electrode was used. The peak marked with an asterisk (*) corresponds to a benzophenone internal standard. Chromatograms for \u003cstrong\u003e1-3\u003c/strong\u003e are shown in the Supplementary Fig. 7. \u003cstrong\u003eb\u003c/strong\u003e, Decay in the concentration of the residual MR-TADF dopants during continuous oxidative bulk electrolysis performed at potentials of 1.04 V vs SCE (\u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e4\u003c/strong\u003e), 1.01 V vs SCE (\u003cstrong\u003e2\u003c/strong\u003e), and 0.98 V vs SCE (\u003cstrong\u003e3\u003c/strong\u003e). The standard deviations were obtained from three independent measurements. The solid lines are linear fits of the initial five data points. \u003cstrong\u003ec\u003c/strong\u003e, Quantum yields for photolysis (red bars) and Faradaic yields for oxidative electrolysis (green bars) of \u003cstrong\u003e1\u003c/strong\u003e-\u003cstrong\u003e4\u003c/strong\u003e. Values are compiled in Table 1. \u003cstrong\u003ed\u003c/strong\u003e, Correlation between \u003cem\u003eLT\u003c/em\u003e\u003csub\u003e95\u003c/sub\u003e and the Faradaic yield for the oxidative degradation of the dopants.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-4184912/v1/5884f2643c242312cecbdd2d.png"},{"id":55287031,"identity":"cd1a24e0-2310-419a-8ee9-42d46d44ee9c","added_by":"auto","created_at":"2024-04-25 08:18:41","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":777866,"visible":true,"origin":"","legend":"\u003cp\u003eDegradation byproduct. a, Mass spectra (ESI, positive) of 100 μM 4 (Ar-saturated THF containing a 0.10 M tetrabutylammonium hexafluorophosphate supporting electrolyte) obtained before (top panel) and after (bottom panel) oxidative bulk electrolysis at an anodic potential of 1.04 V vs SCE. A Pt mesh and a Pt coil were used for the working and the counter electrodes, respectively. A Ag/AgNO\u003csub\u003e3\u003c/sub\u003e pseudo reference electrode was used. The inset structures are the proposed chemical structures corresponding to the indicated \u003cem\u003em\u003c/em\u003e/\u003cem\u003ez\u003c/em\u003e values. The inset black and red bars show the theoretical and observed \u003cem\u003em\u003c/em\u003e/\u003cem\u003ez\u003c/em\u003e values, respectively. b, \u003csup\u003e1\u003c/sup\u003eH NMR (300 MHz, CD\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e) spectra of 4 before (top) and after (middle) the oxidative degradation, and the independently synthesized cyclization byproduct 4' (bottom). c, UV-Vis absorption spectra of 10 μM 4 (Ar-saturated THF containing 0.10 M tetrabutylammonium hexafluorophosphate) obtained during oxidative electrolysis (0-3 h) at an anodic potential of 1.04 V vs SCE. Arrows indicate spectral changes. The inset figure depicts the magnified view in the region 440-750 nm. d, UV-Vis absorption spectra of 100 μM 4 reacted with 1 equiv [FeCl\u003csub\u003e3\u003c/sub\u003e] (Ar-saturated CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e). Arrows indicate spectral changes. The inset figure depicts the magnified view in the region 440-750 nm. e, UV-Vis absorption (top) and absorption difference (bottom) spectra of an Ar-saturated THF 1.1 mM 4' and a 0.10 M tetrabutylammonium hexafluorophosphate supporting electrolyte recorded upon application of an anodic potential of 0.18 V vs Ag\u003csup\u003e+/0\u003c/sup\u003e (a Pt mesh working electrode, a Pt wire counter electrode, and a Ag/AgNO\u003csub\u003e3\u003c/sub\u003e pseudo-reference electrode).\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-4184912/v1/d80d4a65cf141664ed8b3ba2.png"},{"id":55287355,"identity":"c551f924-4572-4201-b8d9-8d45fd362868","added_by":"auto","created_at":"2024-04-25 08:26:41","extension":"jpg","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":54625,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eDegradation mechanism.\u003c/strong\u003e Energy profile for the reaction between the radical cation of the MR-TADF dopant and the radical cation of the HT host. The substituents on dopant and the HT host molecules were omitted.\u003c/p\u003e","description":"","filename":"5.jpg","url":"https://assets-eu.researchsquare.com/files/rs-4184912/v1/b2c11de3510cbf3491322aff.jpg"},{"id":55287030,"identity":"a0eec1a8-45ee-4d9a-9431-9062eddddb14","added_by":"auto","created_at":"2024-04-25 08:18:41","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":355904,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eImproved longevity.\u003c/strong\u003e \u003cstrong\u003ea,\u003c/strong\u003e Liquid chromatograms of 100 μM \u003cstrong\u003e1D\u003c/strong\u003e (Ar-saturated THF containing 0.10 M tetrabutylammonium hexafluorophosphate) obtained during oxidative bulk electrolysis at an anodic potential of 1.04 V vs SCE. A Pt mesh and a Pt coil were used for the working and the counter electrodes, respectively. A Ag/AgNO\u003csub\u003e3\u003c/sub\u003e pseudo reference electrode was used. The peak marked with an asterisk (*) corresponds to a benzophenone internal standard. \u003cstrong\u003eb,\u003c/strong\u003e Decay in concentrations of \u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e1D\u003c/strong\u003e during the continuous oxidative bulk electrolysis. The solid lines are linear fits of the data. The values are Faradaic yields for oxidative degradation of \u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e1D\u003c/strong\u003e. \u003cstrong\u003ec-f\u003c/strong\u003e, Electroluminescence spectra (\u003cstrong\u003ec\u003c/strong\u003e), current density–voltage curves (\u003cstrong\u003ed\u003c/strong\u003e), external quantum efficiencies as a function of current density (\u003cstrong\u003ee\u003c/strong\u003e), and percent luminance decays as a function of operation time of devices of \u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e1D\u003c/strong\u003e driven at a constant current density at an initial luminance of 1000 cd m\u003csup\u003e-2\u003c/sup\u003e (\u003cstrong\u003ef\u003c/strong\u003e).\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-4184912/v1/240165f2fe8f22668ae3f8bf.png"},{"id":72985863,"identity":"2fb826f6-5be8-4d76-99e9-bfbfdabef95a","added_by":"auto","created_at":"2025-01-05 08:06:05","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4161942,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4184912/v1/30c71e84-000d-46e1-9cb1-a69b13512f86.pdf"},{"id":55287032,"identity":"12c362b0-00f1-4038-bc00-b8e2a8452735","added_by":"auto","created_at":"2024-04-25 08:18:41","extension":"pdf","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":6123467,"visible":true,"origin":"","legend":"Supplementary Information","description":"","filename":"Supplementaryinformation.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4184912/v1/6219fa5a9811dd61a4ebc9b8.pdf"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"The Degradation Mechanism of Multi-Resonance Thermally Activated Delayed Fluorescence Materials","fulltext":[{"header":"Introduction","content":"\u003cp\u003eOrganic light-emitting devices (OLEDs) have undergone significant advancements over the past two decades, with notable improvements in efficiency and color purity. These advances are largely due to the discovery of novel emitters, including luminescent molecules capable of exciton harvesting. Among these,\u0026nbsp;cyclometalated complexes of Ir(III)\u003csup\u003e1,2\u003c/sup\u003e and Pt(II)\u003csup\u003e3,4\u003c/sup\u003e, as well as organic\u003csup\u003e5,6\u003c/sup\u003e and organometallic compounds\u003csup\u003e7,8\u003c/sup\u003e that exhibit thermally activated delayed fluorescence (TADF), stand out. The multi-resonance (MR)-TADF emitters, in particular, have attracted considerable attention. For instance, aromatic 1,4-azaborine scaffolds housing complementary boron and nitrogen atoms produce exceptionally narrow fluorescence spectra, accompanied with photoluminescence quantum yields approaching unity.\u003csup\u003e9-11\u003c/sup\u003e The unique emission behavior positions MR-TADF compounds as promising candidates for meeting the demanding requirements of commercial OLED applications.\u003csup\u003e12-17\u003c/sup\u003e\u003c/p\u003e\n\u003cp\u003eDespite their potential, the widespread adoption of MR-TADF molecules is hampered by their instability under the operational conditions in the device. This issue is not unique to MR-TADF molecules. It mirrors challenges faced by earlier generations of phosphorescent and dipolar TADF emitters,\u003csup\u003e18-25\u003c/sup\u003e which also degrade through mechanisms that produce exciton quenchers, charge carrier traps, and non-emissive charge carrier recombination centers, adversely affecting OLED performance. Consequently, a deeper understanding of the degradation mechanisms of MR-TADF materials is crucial for enhancing their operational longevity. Notably, Lee \u003cem\u003eet al\u003c/em\u003e. discovered that TADF-inactive MR fluorescent emitters could achieve longer operational lifetimes than their TADF-active counterparts,\u003csup\u003e26\u003c/sup\u003e a finding echoed by Meng \u003cem\u003eet al.\u003c/em\u003e,\u003csup\u003e27\u003c/sup\u003e who attributed this to the intrinsic instability of long-lived triplet excitons in MR-TADF emitters. In-situ Raman spectroscopy studies suggested that MR-TADF excitons contribute to the morphological instability of emitting layers.\u003csup\u003e28\u003c/sup\u003e Furthermore, Wang \u003cem\u003eet al\u003c/em\u003e. have shown that incorporating an additional boracycle into MR-TADF emitters can extend operational lifetimes, a benefit theorized to stem from increased anionic stability, as supported by quantum chemical calculations.\u003csup\u003e29\u003c/sup\u003e While these studies have proposed various factors contributing to reduced operational lifetimes, direct chemical evidence identifying the specific intermediates and pathways of degradation remains scarce. Given that an OLED\u0026rsquo;s operational lifetime is primarily determined by the intrinsic stability of its components,\u003csup\u003e30\u003c/sup\u003e elucidating the degradation process of MR-TADF molecules is of paramount importance.\u003c/p\u003e\n\u003cp\u003eIn this study, we delve into the intricate chemical mechanisms underlying the intrinsic degradation of a series of blue-emissive MR-TADF molecules, as illustrated in Fig. 1. Through comprehensive chemical analyses, we obtained direct experimental evidence indicating that the primary degradation pathway of MR-TADF materials is initiated by hole trapping. Both experimental observations and quantum chemical computer simulations suggest that the degradation process involves a dehydrogenative cyclization reaction of the radical cationic species. This novel mechanism elucidates the observed enhanced operational stability of a deuterated MR-TADF emitter compared to its undeuterated counterpart, attributing it to the slower dehydrogenative cyclization due to the kinetic isotope effect in the deuterated molecule (\u003cem\u003evide infra\u003c/em\u003e).\u003c/p\u003e"},{"header":"Results","content":"\u003cp\u003e\u003cstrong\u003eOperational stabilities of MR-TADF OLEDs\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eFor this investigation, we selected 5,9-bis(4-biphenyl)-2,12-diphenyl-5,9-diaza-13b-boranaphtho[3,2,1-\u003cem\u003ede\u003c/em\u003e]anthracene (\u003cspan class=\"CitationRef\"\u003e1\u003c/span\u003e), \u003cem\u003eN\u003c/em\u003e\u003csup\u003e7\u003c/sup\u003e,\u003cem\u003eN\u003c/em\u003e\u003csup\u003e7\u003c/sup\u003e,\u003cem\u003eN\u003c/em\u003e\u003csup\u003e13\u003c/sup\u003e,\u003cem\u003eN\u003c/em\u003e\u003csup\u003e13\u003c/sup\u003e,5,9,11,15-octaphenyl-5,9,11,15-tetrahydro-5,9,11,15-tetraaza-19b,20b-diboradinaphtho[3,2,1-\u003cem\u003ede\u003c/em\u003e:1',2',3'-\u003cem\u003ejk\u003c/em\u003e]pentacene-7,13-diamine (\u003cem\u003eν\u003c/em\u003e-DABNA\u003csup\u003e10\u003c/sup\u003e and denoted as \u003cstrong\u003e2\u003c/strong\u003e in this study), 5,9-bis(4-biphenyl)-7-\u003cem\u003eN\u003c/em\u003e-(2-biphenyl)-\u003cem\u003eN\u003c/em\u003e-(4-biphenyl)amino-2,12-diphenyl-5,9-diaza-13b-boranaphtho[3,2,1-\u003cem\u003ede\u003c/em\u003e]anthracene (\u003cspan class=\"CitationRef\"\u003e3\u003c/span\u003e), and 5,9-bis(4-\u003cem\u003etert\u003c/em\u003e-butylphenyl)-2,12-di(\u003cem\u003etert\u003c/em\u003e-butyl)-5,9-diaza-13b-boranaphtho[3,2,1-\u003cem\u003ede\u003c/em\u003e]anthracene (\u003cem\u003et\u003c/em\u003e-DABNA\u003csup\u003e31\u003c/sup\u003e and denoted as \u003cstrong\u003e4\u003c/strong\u003e in this study) shown in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e. The photophysical characteristics of these compounds were assessed using thick films of poly(methyl methacrylate) (PMMA) doped with 2 wt % of the MR-TADF compounds, and the results are summarized in Table\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e. Compounds \u003cstrong\u003e1−4\u003c/strong\u003e displayed pronounced blue fluorescence, with emission peak wavelengths ranging from 459 to 471 nm, full widths at half-maximum (FWHM) values between 775 and 1130 cm\u003csup\u003e−1\u003c/sup\u003e, and photoluminescence quantum yields (\u003cem\u003eΦ\u003c/em\u003e\u003csub\u003ePL\u003c/sub\u003e) from 0.96 to 1.00. The delayed fluorescence lifetimes (\u003cem\u003eτ\u003c/em\u003e\u003csub\u003eDF\u003c/sub\u003es) of these compounds span from 3.8 to 111 microseconds, indicative of moderate energy differences between the singlet and triplet excited states (Δ\u003cem\u003eE\u003c/em\u003e\u003csub\u003eST\u003c/sub\u003e, 0.11−0.27 eV). These photophysical parameters collectively underscore the MR-TADF properties of compounds \u003cstrong\u003e1−4\u003c/strong\u003e.\u003c/p\u003e\n\u003cdiv class=\"gridtable\"\u003e\n \u003ctable id=\"Tab1\" border=\"1\"\u003e\n \u003ccaption\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003ePhotophysical and electrochemical data, and yields for intrinsic degradation of the MR-TADF dopants\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\u0026nbsp;\u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003eλ\u003c/em\u003e\u003csub\u003eeµ\u003c/sub\u003e (nm)\u003csup\u003e\u003cem\u003ea\u003c/em\u003e,\u003cem\u003eb\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003eΦ\u003c/em\u003e\u003csub\u003ePL\u003c/sub\u003e (%)\u003csup\u003e\u003cem\u003ea\u003c/em\u003e,\u003cem\u003ec\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003eτ\u003c/em\u003e\u003csub\u003ePF\u003c/sub\u003e (ns) \u003csup\u003e\u003cem\u003ea\u003c/em\u003e,\u003cem\u003ed\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003eτ\u003c/em\u003e\u003csub\u003eDF\u003c/sub\u003e (µs) \u003csup\u003e\u003cem\u003ea\u003c/em\u003e,\u003cem\u003ee\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003ek\u003c/em\u003e\u003csub\u003er\u003c/sub\u003e\u003csup\u003eTADF\u003c/sup\u003e (10\u003csup\u003e4\u003c/sup\u003e s\u003csup\u003e−1\u003c/sup\u003e)\u003csup\u003e\u003cem\u003ef\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003eE\u003c/em\u003e\u003csub\u003eT1\u003c/sub\u003e (eV) \u003csup\u003e\u003cem\u003ea\u003c/em\u003e,\u003cem\u003eg\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eΔ\u003cem\u003eE\u003c/em\u003e\u003csub\u003eST\u003c/sub\u003e (eV) \u003csup\u003e\u003cem\u003ea\u003c/em\u003e,\u003cem\u003eh\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003eE\u003c/em\u003e\u003csub\u003eox\u003c/sub\u003e (V vs SCE)\u003csup\u003e\u003cem\u003ei\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003eΦ\u003c/em\u003e\u003csub\u003edeg\u003c/sub\u003e (%)\u003csup\u003e\u003cem\u003ej\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eFaradaic yield (%)\u003csup\u003e\u003cem\u003ek\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003e1\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e471\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e96\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e11\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e78\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e5.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.49\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.27\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.98\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.29\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e37\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e467\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e98\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e3.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e6.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.64\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.11\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.92\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.92\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e46\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e461\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e98\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e28\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e5.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.57\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.21\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.97\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.68\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e59\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e459\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e100.\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e111\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e5.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.54\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.25\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.90\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.22\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e79\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003ctfoot\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"11\"\u003e\u003csup\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sup\u003e2 wt % in PMMA films, 300 K. See Supplementary Fig.\u0026nbsp;1 for the UV−Vis absorption and photoluminescence spectra recorded in tetrahydrofuran (THF). \u003csup\u003e\u003cem\u003eb\u003c/em\u003e\u003c/sup\u003eEmission peak wavelength. See Supplementary Fig.\u0026nbsp;2 for the photoluminescence spectra of the PMMA films. \u003csup\u003e\u003cem\u003ec\u003c/em\u003e\u003c/sup\u003ePhotoluminescence quantum yield determined absolutely using an integrating sphere. \u003csup\u003e\u003cem\u003ed\u003c/em\u003e\u003c/sup\u003eLifetime of prompt fluorescence. \u003csup\u003e\u003cem\u003ee\u003c/em\u003e\u003c/sup\u003eLifetime of delayed fluorescence. \u003csup\u003e\u003cem\u003ef\u003c/em\u003e\u003c/sup\u003eRadiative rate constant, \u003cem\u003ek\u003c/em\u003e\u003csub\u003er\u003c/sub\u003e\u003csup\u003eTADF\u003c/sup\u003e = \u003cem\u003eΦ\u003c/em\u003e\u003csub\u003ePL\u003c/sub\u003e /\u003cem\u003eτ\u003c/em\u003e\u003csub\u003eobs\u003c/sub\u003e, where \u003cem\u003eτ\u003c/em\u003e\u003csub\u003eobs\u003c/sub\u003e is the average fluorescence lifetime. \u003csup\u003e\u003cem\u003eg\u003c/em\u003e\u003c/sup\u003eEnergy of the triplet state. \u003csup\u003e\u003cem\u003eh\u003c/em\u003e\u003c/sup\u003eThe energy difference between the singlet and the triplet excited states. Refer to Supplementary Fig.\u0026nbsp;3 for details. \u003csup\u003e\u003cem\u003ei\u003c/em\u003e\u003c/sup\u003eOxidation potential determined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) for Ar-saturated THF containing 1.0 mM dopant and 0.10 M tetrabutylammonium hexafluorophosphate; A glassy carbon disk and a Pt wire for the working and counter electrodes, respectively; a Ag/AgNO\u003csub\u003e3\u003c/sub\u003e pseudo reference electrode; scan rates = 0.1 V s\u003csup\u003e−1\u003c/sup\u003e (CV) and 4 mV s\u003csup\u003e−1\u003c/sup\u003e (DPV). See Supplementary Fig.\u0026nbsp;4 for the voltammograms. \u003csup\u003e\u003cem\u003ej\u003c/em\u003e\u003c/sup\u003eQuantum yield for photolysis. \u003csup\u003e\u003cem\u003ek\u003c/em\u003e\u003c/sup\u003eFaradaic yield for oxidative bulk electrolysis.\u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tfoot\u003e\n \u003c/table\u003e\n\u003c/div\u003e\n\u003cp\u003eThe electroluminescence performances of compounds \u003cstrong\u003e1−4\u003c/strong\u003e, utilized as dopants, were assessed using a specific device configuration, comprising an indium tin oxide (ITO) anode, a hole-injection layer of \u003cem\u003ep\u003c/em\u003e-doped (3 wt% NDP series, Novaled AG) \u003cem\u003eN\u003c/em\u003e-([1,1′-biphenyl]-4-yl)-9,9-dimethyl-\u003cem\u003eN\u003c/em\u003e-(4-(9-phenyl-9\u003cem\u003eH\u003c/em\u003e-carbazol-3-yl)phenyl)-9\u003cem\u003eH\u003c/em\u003e-fluoren-2-amine (BCFA) (10 nm), a hole-transporting layer of BCFA (135 nm), an electron-blocking layer of 2,2′-di(9\u003cem\u003eH\u003c/em\u003e-carbazole-9-yl)-1,1′-biphenyl (oCBP) (5 nm), an exciton-blocking layer of 3′,5′-di-9\u003cem\u003eH\u003c/em\u003e-carbazol-9-yl-[1,1′-biphenyl]-2-carbonitrile (mCPD) (5 nm), an emission layer (40 nm), a hole-blocking layer of 9-(3-(9\u003cem\u003eH\u003c/em\u003e-carbazol-9-yl)phenyl)-9\u003cem\u003eH\u003c/em\u003e-carbazole-3,6-dicarbonitrile (mCP-2CN) (10 nm), an electron-transporting layer co-deposited with dibenzo[b,d]furan-2,8-diylbis(diphenylphosphine oxide) (DBFPO) and lithium 8-hydroxyquinolinate (LiQ) (22 nm), an electron-injecting layer of LiQ (9 nm), and an aluminum (Al) cathode (100 nm). The emission layer, comprising a 1.5 wt % dopant, utilized a ternary composition including a 9-(3-biphenyl)-3,9′-bicarbazole hole-transporting (HT) host, a 3′-(9-(3-cyanocarbazolyl))-5′-cyano-3-(9-carbazolyl)biphenyl electron-transporting (ET) host, in a volumetric ratio of 6:4. The chemical structures and energy levels of the constituent materials are displayed in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ea. Electroluminescence spectra, recorded at an intensity of 1000 cd m\u003csup\u003e−2\u003c/sup\u003e, revealed peak wavelengths of 474 nm for compounds \u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e2\u003c/strong\u003e, 465 nm for compound \u003cstrong\u003e3\u003c/strong\u003e, and 462 nm for compound \u003cstrong\u003e4\u003c/strong\u003e, as shown in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003eb. The FWHM values as small as 890−1300 cm\u003csup\u003e−1\u003c/sup\u003e and the Commission internationale de l'éclairage coordinate y values (CIE\u003csub\u003ey\u003c/sub\u003e) approaching 0.10 demonstrate the validity of the MR-TADF molecules as blue emitters.\u003c/p\u003e\n\u003cp\u003eThe devices incorporating \u003cstrong\u003e1−4\u003c/strong\u003e demonstrate negligible differences in their current density profiles, as depicted in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ec. This uniformity can be attributed to the similar energy offsets between the highest occupied molecular orbitals (HOMOs) of \u003cstrong\u003e1−4\u003c/strong\u003e and the HT host ranging from 0.4 to 0.5 eV. The maximum external quantum efficiency (\u003cem\u003eEQE\u003c/em\u003e\u003csub\u003emax\u003c/sub\u003e) across these devices is identified to lie between 22.5 and 26.7% (Table\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e). Figure\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ed reveals that devices based on compounds \u003cstrong\u003e1\u003c/strong\u003e, \u003cstrong\u003e3\u003c/strong\u003e, and \u003cstrong\u003e4\u003c/strong\u003e experience moderate \u003cem\u003eEQE\u003c/em\u003e roll-off, whereas the device utilizing compound \u003cstrong\u003e2\u003c/strong\u003e shows a relatively suppressed roll-off due to the significantly shorter delayed fluorescence lifetime (\u003cem\u003eτ\u003c/em\u003e\u003csub\u003eDF\u003c/sub\u003e) of 3.8 µs, compared to 28−111 µs for the other MR-TADF compounds. These varying roll-off profiles hint at the presence of triplet−triplet annihilation or triplet−polaron annihilation processes, which are recognized for generating unstable species that shorten device operational lifetimes.\u003csup\u003e30,32,33\u003c/sup\u003e Nonetheless, there appears to be no direct correlation between the operational stability and \u003cem\u003eEQE\u003c/em\u003e roll-off behaviors (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ee). For instance, devices of \u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e3\u003c/strong\u003e, despite showing substantial \u003cem\u003eEQE\u003c/em\u003e roll-off, exhibit \u003cem\u003eLT\u003c/em\u003e\u003csub\u003e95\u003c/sub\u003e (the time at which luminance decreases to 95% of its initial value at 1000 cd m\u003csup\u003e−2\u003c/sup\u003e) values of 4.3 and 2.9 h, respectively, comparable to the 3.2 h of device \u003cstrong\u003e2\u003c/strong\u003e that has the least \u003cem\u003eEQE\u003c/em\u003e roll-off. Moreover, device \u003cstrong\u003e4\u003c/strong\u003e, despite having an \u003cem\u003eEQE\u003c/em\u003e roll-off profile similar to that of devices \u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e3\u003c/strong\u003e, presents the shortest \u003cem\u003eLT\u003c/em\u003e\u003csub\u003e95\u003c/sub\u003e value of only 0.6 h. This observation suggests that the lifetime of these devices may not be predominantly determined by the bimolecular annihilation processes involving excitons.\u003c/p\u003e\n\u003cdiv class=\"gridtable\"\u003e\n \u003ctable id=\"Tab2\" border=\"1\"\u003e\n \u003ccaption\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eDevice performance\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\u0026nbsp;\u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003eV\u003c/em\u003e (V)\u003csup\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003eJ\u003c/em\u003e (mA cm\u003csup\u003e−2\u003c/sup\u003e)\u003csup\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eCIE (x, y)\u003csup\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eEQE (%)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003epower efficiency (lm W\u003csup\u003e−1\u003c/sup\u003e)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003eLT\u003c/em\u003e\u003csub\u003e95\u003c/sub\u003e (h)\u003csup\u003e\u003cem\u003ec\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003e1\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e5.14\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e7.00\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e(0.11, 0.17)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e25.1\u003csup\u003e\u003cem\u003eb\u003c/em\u003e\u003c/sup\u003e / 12.3\u003csup\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e30.9\u003csup\u003e\u003cem\u003eb\u003c/em\u003e\u003c/sup\u003e / 8.79\u003csup\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e4.3\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e5.38\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e5.75\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e(0.11, 0.15)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e23.7\u003csup\u003e\u003cem\u003eb\u003c/em\u003e\u003c/sup\u003e / 17.4\u003csup\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e21.3\u003csup\u003e\u003cem\u003eb\u003c/em\u003e\u003c/sup\u003e / 10.2\u003csup\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e3.2\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e5.25\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e5.25\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e(0.13, 0.11)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e26.7\u003csup\u003e\u003cem\u003eb\u003c/em\u003e\u003c/sup\u003e / 16.8\u003csup\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e24.5\u003csup\u003e\u003cem\u003eb\u003c/em\u003e\u003c/sup\u003e / 9.19\u003csup\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.9\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e6.11\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e6.11\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e(0.13, 0.10)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e22.5\u003csup\u003e\u003cem\u003eb\u003c/em\u003e\u003c/sup\u003e / 5.8\u003csup\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e20.0\u003csup\u003e\u003cem\u003eb\u003c/em\u003e\u003c/sup\u003e / 2.57\u003csup\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.60\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003ctfoot\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"7\"\u003e\u003csup\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sup\u003eValues at a luminance of 1000 cd m\u003csup\u003e−2\u003c/sup\u003e. \u003csup\u003e\u003cem\u003eb\u003c/em\u003e\u003c/sup\u003eMaximum values. \u003csup\u003e\u003cem\u003ec\u003c/em\u003e\u003c/sup\u003eOperation time when the luminance decreases to 95% of its initial value at initial luminance of 1000 cd m\u003csup\u003e− 2\u003c/sup\u003e. See Supplementary Fig.\u0026nbsp;5 for plots of the luminance and power efficiency as functions of current density.\u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tfoot\u003e\n \u003c/table\u003e\n\u003c/div\u003e\n\u003ch3\u003eDegradation intermediates\u003c/h3\u003e\n\u003cp\u003eTo elucidate the degradation mechanisms of MR-TADF dopants, we conducted both photolysis and bulk electrolysis experiments. These experiments aimed to simulate the excitonic and polaronic degradation pathways, respectively, facilitating the identification of crucial degradation intermediates. Photolysis was performed in argon-saturated tetrahydrofuran (THF) solutions containing 100 µM of compounds \u003cstrong\u003e1\u003c/strong\u003e − \u003cstrong\u003e4\u003c/strong\u003e, under continuous illumination with monochromatic light of 450 nm wavelength (photon flux = 4.0 × 10\u003csup\u003e8\u003c/sup\u003e einstein s\u003csup\u003e− 1\u003c/sup\u003e). The progression of photolytic degradation was monitored using high-performance liquid chromatography (HPLC) due to the inadequacy of UV − Vis absorption spectroscopy for quantitative analysis. The quantum yield for degradation (\u003cem\u003eΦ\u003c/em\u003e\u003csub\u003edeg\u003c/sub\u003e) was determined to be under 1% (Table\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e and Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ec), and importantly, \u003cem\u003eΦ\u003c/em\u003e\u003csub\u003edeg\u003c/sub\u003e exhibited no significant correlation with \u003cem\u003eLT\u003c/em\u003e\u003csub\u003e95\u003c/sub\u003e, suggesting that unimolecular excitonic degradation does not primarily influence the operational stability (for additional details and discussion, see Supplementary Fig.\u0026nbsp;6).\u003c/p\u003e\n\u003cp\u003eIn marked contrast, radical cation forms of the MR-TADF molecules demonstrated pronounced instability during oxidative bulk electrolysis at anodic potentials, as quantified by HPLC (detailed in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ea, \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003eb, and their captions). Reductive bulk electrolysis was not considered, given the electron-scattering nature of the MR-TADF molecules, as inferred from the positions of their lowest unoccupied molecular orbitals (LUMOs) illustrated in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ea. By contrast, the MR-TADF compounds can trap hole carriers from the HT host with driving forces of 0.4−0.5 eV. The Faradaic yields for oxidative bulk electrolysis, representing the ratio of decomposed compound quantity to the electrons transferred, were significantly higher by two orders of magnitude compared to \u003cem\u003eΦ\u003c/em\u003e\u003csub\u003edeg\u003c/sub\u003e (as shown in Table\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e and Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ec). Although these solution-based experiments do not perfectly mimic the polaronic degradation in the emissive layers, they underscore the notably lesser stability of the MR-TADF compounds' radical cations compared to their excitons. Moreover, an inverse correlation was observed between \u003cem\u003eLT\u003c/em\u003e\u003csub\u003e95\u003c/sub\u003e and the Faradaic yield (see Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ed). While not definitive, this negative linear relationship implies a close association between the positive polarons of MR-TADF molecules and the operational stability of OLEDs.\u003c/p\u003e\n\u003cp\u003eThe observed relationship between the operational stability of OLEDs and the stability of MR-TADF molecules is further supported by examining the behavior of trapped hole carriers within these dopants. The ideality factor [(\u003cem\u003ek\u003c/em\u003e\u003csub\u003eB\u003c/sub\u003e\u003cem\u003eT\u003c/em\u003e/\u003cem\u003eq\u003c/em\u003e)⋅(∂ln \u003cem\u003eJ\u003c/em\u003e/∂\u003cem\u003eV\u003c/em\u003e)]\u003csup\u003e−1\u003c/sup\u003e for devices using compounds \u003cstrong\u003e1−4\u003c/strong\u003e consistently exceeds two, as shown in Supplementary Fig.\u0026nbsp;8, where \u003cem\u003ek\u003c/em\u003e\u003csub\u003eB\u003c/sub\u003e is the Boltzmann constant, \u003cem\u003eT\u003c/em\u003e is the absolute temperature, \u003cem\u003eq\u003c/em\u003e is the elementary charge, \u003cem\u003eJ\u003c/em\u003e is the current density, and \u003cem\u003eV\u003c/em\u003e is the voltage. This finding suggests significant charge carrier trapping within the MR-TADF molecules.\u003csup\u003e34\u003c/sup\u003e In single carrier devices designed for exclusive hole transport, the hole current density profiles vary according to the specific MR-TADF dopant used, as depicted in Supplementary Fig.\u0026nbsp;9. The sequence of hole trapping within the dopants is observed to follow the order \u003cstrong\u003e2\u003c/strong\u003e \u0026gt; \u003cstrong\u003e4\u003c/strong\u003e ~ \u003cstrong\u003e3\u003c/strong\u003e \u0026gt; \u003cstrong\u003e1\u003c/strong\u003e. This order, conjunction with the Faradaic yield data, offers a coherent kinetic rationale for the observed \u003cem\u003eLT\u003c/em\u003e\u003csub\u003e95\u003c/sub\u003e values of the OLED devices. This rationale is predicated on the assumption that the degradation rate adheres to pseudo first-order kinetics, with the rate equation modeled as rate = \u003cem\u003ek\u003c/em\u003e⋅[\u003cstrong\u003eD\u003c/strong\u003e\u003csup\u003e•+\u003c/sup\u003e] = exp(−\u003cem\u003eE\u003c/em\u003e\u003csub\u003ea\u003c/sub\u003e/\u003cem\u003ek\u003c/em\u003e\u003csub\u003eB\u003c/sub\u003e\u003cem\u003eT\u003c/em\u003e)⋅[\u003cstrong\u003eD\u003c/strong\u003e\u003csup\u003e•+\u003c/sup\u003e], where \u003cem\u003ek\u003c/em\u003e is the rate constant for degradation, [\u003cstrong\u003eD\u003c/strong\u003e\u003csup\u003e•+\u003c/sup\u003e] is the molar concentration of the radical cation of an MR-TADF dopant, and \u003cem\u003eE\u003c/em\u003e\u003csub\u003ea\u003c/sub\u003e is the activation energy for the rate-determining step. Under this framework, the device utilizing compound \u003cstrong\u003e1\u003c/strong\u003e exhibits the longest \u003cem\u003eLT\u003c/em\u003e\u003csub\u003e95\u003c/sub\u003e, attributable to molecule \u003cstrong\u003e1\u003c/strong\u003e having the smallest Faradaic yield, indicative of the highest intrinsic stability, and the lowest density of positive polarons, leading to the lowest concentration of the degradation intermediates. Conversely, the notably shorter \u003cem\u003eLT\u003c/em\u003e\u003csub\u003e95\u003c/sub\u003e for the device incorporating compound \u003cstrong\u003e4\u003c/strong\u003e can be explained by its high Faradaic yield and dense population of positive polarons, highlighting a direct correlation between these factors and device longevity.\u003c/p\u003e\n\u003ch3\u003eDegradation mechanism\u003c/h3\u003e\n\u003cp\u003eTo shed light on the degradation mechanism of MR-TADF materials, we analyzed a byproduct formed from radical cations. Electrospray ionization (ESI) mass spectrometry in positive mode revealed a significant peak at an \u003cem\u003em\u003c/em\u003e/\u003cem\u003ez\u003c/em\u003e value of 810.51 amu in an electrolyzed solution of compound \u003cstrong\u003e4\u003c/strong\u003e, as shown in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ea. This peak corresponds to a species involving [\u003cstrong\u003e4\u003c/strong\u003e − 2H], precisely matching with the theoretical isotope distribution. Notably, the pristine sample of \u003cstrong\u003e4\u003c/strong\u003e lacks this peak, underscoring that the cyclization product specifically arises from the radical cation state. This structural assignment gains additional support from the appearance of new peaks in the \u003csup\u003e1\u003c/sup\u003eH NMR (300 MHz, CD\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e) spectrum, indicative of a non-symmetric aromatic framework formation, as depicted in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003eb. An independently synthesized non-symmetric cyclization compound (labeled as compound \u003cstrong\u003e4′\u003c/strong\u003e, see Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003eb) shows \u003csup\u003e1\u003c/sup\u003eH NMR peaks corresponding to those observed in the oxidation byproduct. This observation aligns with known electrochemical intramolecular C − C coupling reactions among radical cations of various arylamines.\u003csup\u003e35,36\u003c/sup\u003e\u003c/p\u003e\n\u003cp\u003eFurther evidence for the intermediacy of the radical cation in the cyclization reaction comes from spectroelectrochemical measurements. Upon applying an anodic potential of 1.04 V versus a saturated calomel electrode (SCE) to an argon-saturated THF solution containing 10 µM of compound \u003cstrong\u003e4\u003c/strong\u003e and 0.10 M tetrabutylammonium hexafluorophosphate as supporting electrolyte, a broad absorption band appears in the 500 − 700 nm region (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ec). This absorption signature is replicated upon the electrochemical oxidation of \u003cstrong\u003e4\u003c/strong\u003e with [FeCl\u003csub\u003e3\u003c/sub\u003e] as a strong oxidant (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ed), signifying that the visible absorption band originates from the radical cation of a cyclized compound. This is corroborated by the identical absorption band observed upon the electrochemical oxidation of compound \u003cstrong\u003e4′\u003c/strong\u003e at a potential of 0.18 V vs Ag\u003csup\u003e+/0\u003c/sup\u003e (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ee). Collectively, our experimental findings converge on the oxidative cyclization as a pivotal degradation pathway of the MR-TADF molecule.\u003c/p\u003e\n\u003cp\u003eQuantum chemical calculations on the oxidative degradation of compounds \u003cstrong\u003e1\u003c/strong\u003e–\u003cstrong\u003e4\u003c/strong\u003e suggest heterobimolecular hydrogen atom abstraction, followed by cyclization, as the most likely degradation pathway, in good agreement with experimental evidence. Initial exploration into unimolecular reactions, where bond cleavage might lead to degradation, showed that the C–C single bonds in the neutral dopant molecule strengthen upon oxidation. This is due to the antibonding character of the HOMO in the neutral compound between π-conjugated fragments, which increases bond order upon one-electron oxidation (Supplementary Table\u0026nbsp;1). Consequently, unimolecular processes are unlikely to be the primary degradation pathways for these emitter molecules. Subsequent investigation into bimolecular reactions identified intermolecular hydrogen atom transfer (HAT) as a key step, initiated by electrogenerated radical species.\u003csup\u003e37\u003c/sup\u003e The reaction free energies for HAT, detailed in Table\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e, reveal that hydrogen atom abstraction from the radical cation of the MR-TADF compound (reaction \u003cstrong\u003ea\u003c/strong\u003e) is energetically favorable, with free energy values between 4.9 and 7.8 kcal mol\u003csup\u003e−1\u003c/sup\u003e. This contrasts with hydrogen atom addition to the radical cation (reaction \u003cstrong\u003eb\u003c/strong\u003e), which is less favorable, exhibiting energies between 8.9 and 15.6 kcal mol\u003csup\u003e−1\u003c/sup\u003e. The favored reaction leads to the formation of a fused five-membered ring via the C–C bond formation, \u003cem\u003eortho\u003c/em\u003e to the nitrogen atom. This process, culminating in extended π-conjugation within the cyclized product, significantly contributes to its energetic stabilization, thereby rendering the reaction irreversible and highlighting oxidative cyclization as a pivotal degradation mechanism in MR-TADF materials.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eTable 3.\u003c/strong\u003e Free energy change for hydrogen atom transfer reactions of the radical cation of MR-TADF dopants\u003cem\u003e\u003csup\u003ea\u003c/sup\u003e\u003c/em\u003e\u003c/p\u003e\n\u003cp\u003e\u003cimg 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jz322LqKGFns6ihBasuWLdUdd9yRI0pdVq9cQxbGWMxKMFcJIDis3vCWAk/9CFxwwQXVtm3b+jPN6ex1111X/cf/+B/n1Jo3k4sAkxj5sNy6css//PDD9SQ0t55VLu+EdMLaJ1hyD8sYku7vG4MsY5YB4sYlJhKXmSBRMUlECb3HELe2Nqz9qN62fF3HdLmV/pQgpFyGJ7GNvdzNKr1WTQhSuUl4gFGsLMLD6jpXnmUuL7zG0Edsp4T9jKEvqyDDmMaY9aergP0s+uiEdBaozqnOMQ0AJ6RhSs91oCJKYyCk6nEJQmHtJ4WQSpZShEI4q96YrfDI1XVMm1POK7zG0IdS9jOGvqyCDGMaY2OKx1PVvRPSqWpu32VWXyGdlgJzHaiIkhPSdr2XIhTCub2V/qMiWLm67m9lec4KrzH0qJT9jKEvqyDDmMaYE9J8i3NCmo/hwmoY0wCwK1wLA2QCDec6UBElJ6Ttyi5FKIRzeyv9R0WwcnXd38rynBVeY+hRKfsZQ19WQYYxjbExxeOp6t4J6VQ15yukk9RcrgMVUXJC2q7+UoRCOLe30n9UBCtX1/2tLM9Z4TWGHpWynzH0ZRVkGNMYc0Kab3FOSPMxXFgNYxoAvkIaZga5DlREyQlpO96lCIVwbm+l/6gIVq6u+1tZnrPCaww9KmU/Y+jLKsgwpjE2png8Vd07IZ2q5nyFdJKay3WgIkpOSNvVX4pQCOf2VvqPimDl6rq/leU5K7zG0KNS9jOGvqyCDGMaY05I8y3OCWk+hgurYUwDwFdIw8zAOlA+gRf7iTu+EkQqTUhVb1gv9n4djK9xkUoQCms/fOWIl6aHJt5FCpazeO0TL8KPeQcpMvNSdcam1XVoX1YxXwn7KYWbE9JSSM6nnjGNsTHF4/mgX74VJ6TlMZ1bjX/zN3/jL8afG9plGuIF4P/u3/27ujJIGEQKcsnL1EMTxIsvyvzZn/1ZaJHWfJCtI488MupdqG1fazrvvPOyX2zOhxUOOeSQtc/htgrcOKgv/divNV188cUVfzmJl9qzQkr9YD30adWutnhJP+TaUz8CvBj/e9/7Xn+mOZ3lxfg33XTTnFrzZnIRYGx+/OMfz62mSPkxxeMiHVpAJU5IFwB6iSbH+OlQvmjT953vEv2eeh2QHQIeWPHFIxIza3C7+eabBwmZPtP6mc98Zq1MzGoi7ekzicjAl4Tsd+G78LVlmnITxDmfm/70T/+0lgXb7ktaCbVyQ+gh9hdddFH9F0vy1R5tUy86YsuKGe2BMfoJsW9NNM4///xqx44dqtq3DQQ0ofBPhzaA8Z+DCMgH8Onjk046aRSfDh3Lp7wHwRtxBiekI1ZOm2j6bKP91nLbsbaypY+JBLDKRxAm2WOxRKm0fGOur22lkRVLSFAbIbO4Cmv6RxmIJSsFOOmh1NaGiIFdabT1iKRJLhGuVNJn627utxFfm4evQ4UQRUvyQ+yQ/OBox5WCHu3pq1RWD816kT3lc7C2f6uw34Zr27F5YdG0b9ptOzYvebydfgSaPoDcbcf6aylzti32th0r09ry1+KEdCI6FgngEiBkhgS54B4apXk5UQJxc7WIQUgwVmIlzxIHHfftegTkvHSfoggZxIfUhvX6GvaueIoIUY7LzRAskh7O4fjQKqz9LrzIFuVE0uZJuCxhFwFHJu43ZAuBCbmULsLOOLniiiuqrVu31riw/9xzz9Uru7ptQuOqiS/tcb+sJezYN+0rERBjJgYqt2rbJnEAW3wJW5KwnsVkp4m1xl7TvjX2NBbRK3k9LRYB9IJdMBaxE/kA6Waek5oxxePFaqVs605Iy+JZvLY2EiDi0HaJd5ZOVA4AB02gJ1ni0Azo83QQxYGfc4VNctWG9ZBIOEn+IKHc10myhFSBdqgeyFuTXInYha7EDrURel6kQYSdcrptwR7rq48xQd8hoeCxe/fuel+ElPpCksadAiJl2o6F1LVqeZo4Wfu2k2rhErvCrXIh2zafZScUzTra8jfz+O/ZIaBJi71dBr/Ab3wAtmSTJjV2AmnP5+yPKR7n9GOsZZ2QjlUzVVX98Ic/XEcMYgaanOiFF15Y7dq1K7uXctgiATHEV3KfffbZfk9djybkeE855ZTqxBNPrJ0tOMcmSNddd91V/4mQxtYhx8v9fax021Ws2Lpy84u8gMkJJ5xQPwimVdOYuiGk4MJWK6Qx5ZWXsQAukP5ZBD21swxbfM+VV165DqeYCYUmQl/72tey4cCmm/dvN4lyXyOaHN1yyy192fxcQQTQe+gCSLNZ6fbqq68uco/7mOJxs6/L8tsJ6Yg1CZmApBCQebjC3ssWKvZnP/vZ6gtf+EJo9s58hx12WLV9+/b6fOqtAV/96lf9qeNOhF8/8dRTT1U7d+58/UDkHnbz2muv1YQplZCqSYgoDz6NIfEkNk9kpyaR0BtvvLFeKWWFNDUxJu++++7U4itTDt/z27/923V/dcnV3nMeAgRE8tBDD614E0NOsm+40CQ5ZUJx8sknV08++WSOKF42AAH0jd7RP3/cWpFy+wQ+A93npjHF49y+jLW8E9KxasZcbmVVUk/7horLvXYEgFLv1YMMsyoFGdU9V6GyIAOrIlyaQy5Ps0VAJPSJJ55Yu2Sf2mIp+0lt35bLtR8RUi7Zg1EOIbVy+X43ArIfCDz3v+ve5u4Sr5+BNOq1WfI/r5+N37P2Q72sdMckLhGTuI8xph8xbXje1xEg3qB3EnGD2BOT0DE2RNm220Ji6iKv/OoY4nGs7FPJ74R0xJrSAEgRUU5TASGlDlsmJyDIIdiAYOv2/fEiUMp+SvTQ7acEivOtI8d+LCHJ8T/qca79yB/Lt6pe384GAav/lBZkM4o/KXXYMtK/PRa6L5vJGQ+hbU05nxPSEWtvTANAgzsFLjmE3ICQ0vYql8H55aYxOdBS9sN9iayceJo9Ajn2YwlJjv9RL3PtR/5Y5EL1+nY2CFj9p7Qgm1H8SanDlpH+7bHQfdlMzngIbWvK+ZyQjlh7YxoAGtwpcMkh5AaElLZXuUyO/Qi3MTnQUvaj4KA++nZ2COTYjyUkOf5Hvcu1H40ntx8hOtut1X9KS7IZxZ+UOmwZ6d8eC92XzeSMh9C2ppzPCemItTemAaDBnQKXHEJuQEhpe5XL5NiPcBuTAy1lPwoO6qNvZ4dAjv1YQpLjf9S7XPvReHL7EaKz3Vr9p7Qkm1H8SanDlpH+7bHQfdlMzngIbWvK+ZyQjlh7YxoAGtwpcMkh5AaElLZXuUyO/Qg3HiSwL4DX8UVseTCOp/5zk4JDbj1efhiBnABsCUmO/5GUuf5H48ntR4jOdmv1n9KSbEbxJ6UOW0b6t8dC92UzOeMhtK0p53NCOmLtjWkAaHCnwCWHkBsQUtpe5TI59sP7Oimvv0U+kV5aFgWHVbaNefU9JwBbQpLjf9TXXP+j8eT2I0Rnu7X6T2lJNqP4k1KHLSP922Oh+7KZnPEQ2taU8zkhHbH2NAB4xUjsQxilB4AGN6+San6RaQhCOYTcgDDUjp9fj4DsZ/3RsF96sT65N2/eXL9QPqxk+VylZdHYKC+p19hEQAGY1z7FvmbJEhL5n2b9Mb+t/2G1HZliksaT208Maul5rf75KAHvIo1JshnFn5iybXml/zHE4zb5luGYE9IRa9EOAAYXzj3UifKVCvJu2bKluv3227N7edRRR9XvIYWQ8nLimHeRUgZnQkAYy0vWswFpqQC8x/SydNlPi6iDh0qvSoJLqO02hSstC1/CGsuLzXM/gtDEamy/77jjjtoHoXtut7CffwyRVe/7lP8JKdOVB//DV6NI+rhHDEmWLHyhS/tdbfnxfAQgpMcee2xdEXoiBsa8i1Q6uuqqq6p77703WyD5U+pNjceMB/48tSPghLQdl1EcPe200+rPJLI6ikOHkDIQmN2HJAYxX7rgL2Yg27ohkgSSd7zjHdX555+/tjoqhx5aL4OYzz6WIMdWvrHsg/VYPiepTxz++q//etKXTcDUrkrygn1eKp+S9Pm+c889t7bdGAKg9krJos/pnnTSSdVxxx2XPCYkV86WMc24yv1MbI4M8yjLRGTjxo1rWDM5ZYUx9GtNTf9D+ZSE/0Hn+DFN7NHBNddcU3/WNKRe+WD689JLL6WI4WUiEABvdMY4wQ7409eaRDaHqiM+oXN0luJ7qB87wV4PPvjg7HiMHGNatBjCb97nnZDOG/HI9iCfdjamwYFT73Kicvo4W/LbgQxZCU0inby3kYQTsKujIfUyy2UwI2/spf5QOReZT4RLWCNL27F5yCjCxRdKhHXbsSFZ0FlzVRJSSgp16jbYgwep7Vh9oudfnyyhl13b7LTtWI8YxU4RZHlIzH6f2x5jFW/ZkrC2q6PoDgz46g3n21Kb/6EOEZS2Ms1j1l8yFkQqaVsTe+xT9ZK/LUlekdm2PH5sNggQf+zqKHocmtQQq9CpruSl+B7Zil0Ewg5y4/FsUFqOWp2QTkCPGhjWiWrAiSzSDRw7zto6fts9kRMIIgN069at9coXq1/cJ6ikujWYdVxbBQq2JNVLfqU2mXVuGbZtDg5nZZ9Ih7yhM46Bx6wSeiewo3c74eDeKXRJ0qppl07JIyItvbbJSzv0ybZj89FPES5LXmnXEgC+IW5JvK2DfdkUttqVZIe2nWZexgfy2j4hn8aN2rEkvllHqd8iNSJhImqaWGJT6Czl++qlZJxlPZooy/9YW2HioTTkfyxBYaUS/6U/PXwn/2PJhOpn2zZRlq1oAkU+7GOI/Nh6fX82CGis2Nim8SS/QsuMIS2AaFxZieTjNKmR3bB98MEH17Kq7rYJiGwrNx6vNeY7awg4IV2DYvw7bU6UAUhScFag7esNg42grEGIE+cyJltWaPpWX1Vvm4PgGIn67SxSZZZhK2dE/0SEmoHW9hNMROKs47R5cvYVRNtIr5VLAV92YglaG7nuk6mLxMmJi3DZOqztKlCAX9NOZFd9pNfW2yW7SA2BR2NE5fjdnLiFEHaVj92G6kH1Kmj2EXblneK26R+kH7Z9ZML2VXbyl3/5lxX3dOK7WNXHpzFGIS5tZMLWwT52gq1poka9lFf9nNOkrlnWf88fATuWsBfpyvrlED+L3yTWcV8otoOOdY8odoMdymd29dL6NHwiSbYsPxsSj7vqX8XjTkgnqHXrRB999NF1DjWmOzhvnDlbBuNrr70WU7zOax3EM888s7aaoIEZXeGIC/zFX/zFOgJFH5vEpkt8OS/uw92xY0dXtuDjPAxD0G0jXM1KmkTRBlseMrPkulm277dIHMQJOwpx4tiuldsGkt/5nd+pZbFkua99e04kbtOmTdVFF10UNKmytqvgo0Dywx/+0FaftA/O1113Xd1fkRphJgLUV7EI+9e+9rW+bJM8Z/X+wAMPRN8fr05DJvBd+DAm1ZDSlCS9s7X7KXV5mdkjYCc12E9zYhsqgWxHcTC0nM1XKh7bOld13wnphDV/66231jdaa3YW2xWcOJcpcOo33njjuksWsXXxFONb3vKWpV5NwHlpVq7L0rEzYN56wOXh3MQDb/fdd19wNRCApszIfuSRR2bfTsDDUxDjmETbrD5pZfev//qvqwMPPLDzfsLQui+88MLq4osvDs1e52sj7Og6N23btq0m6tTTtao81AZ646HEF198cSjrJM8zno455pjqU5/6VJId4ru0QgoxyNEbE4gPfOAD9R/7nsaNAGMDu8F+UhdAsBdsiD8mNDkPqxGPN2zYUI/1cSM3Xunyve54+7b0kuGAubyemporpFrFSamPFSZmqcucFOwgU22Xpfv6zooY+HKZiPsEcxN6pz5Wc2IehNGqLiQs137UB73njzq53BWaCPrgCJ7bt2+v3vCGN4QW7cxH+/yx+hmDswi75JeuOxsKOCFdUzf66rrvtq0qsNHYZlxpBbct79SPyX5S+gGRQFfyZZDTnCT7yanDy84PAY2x1BZlO9gP+7t3706tqpg/TRZgCQo6IZ2wEnMJBbNBzQ5zBjVKHmoAACAASURBVCIQrhIhTTEZBd1cB6q2RUhzAmiu/UiWEn0rTUhz+1aSkAqnmK0dT05Iu5HjNiP5MLa5KWc85bbt5eMRyPWn1nZSblmzEuf6HFvXqu47IZ2w5ksNgNTLHRY6G0Dt8WXazyEpJUibxdIJqUXj9X0RityxkaNrSZMTLO14ckIqRPu3JfyY7Ke/JT87FgRyxpjtQwnbyfU5Vp5V3XdCOmHNlxoAkCU9MZ4Khw2gqXWMvVwOSVk4IeW1U7xPlkvq+16xU9J+CAw5wcFXSNdbvx1PTkjXY9P2C0IBTrnJCWkugvMtn+NzrKTcz86Yy0ml/GmODFMv64R0whosNQBElnKgsAE0p54xl50sIX355WrPGWdUe3jw6Otfr/a8731Vdf/9xe55kv3kBAcnpOst344nJ6TrsWn7ZfFqOx96zAlpKFLjyJfjc2wPSoyxUvHYyrVq+05IJ6zxUgNAhCIHilIBIUeGWZedKiHdw1P9fKGLl+SzQvrLX9YE9b//l/+y9uBMDnayn5zg4IR0vQbseCoRLNfXPq5fsp8cqSxeOfU4Ic1Bb/5lc3yOlbbEGCsVj61cq7bvhHSCGucBJF7XxJO4//k//+dKn3XcryuvvFLtue22qiYk+z7/uV+eqqqfRmZgpyTJwpPEPC3dKUtK5SMrM1lCetBBVXXvvXtXSd/97r02cf311Qtbtjgh7bCxHF2rypxgaQlWiWApmca0xVfwYCWBnFeYdT5Y+Q//UO255pq9K/z7XkDe7IfFq3ku5Ldk4e0MP/jBD7plCanM88wcAR5Gwm7QO++H7nyg7YUXarvZwxffHnqoU66cMaYYOBiPO1v3E0LACamQmNCWwUfAxImyzysr9ktcpuXS7LZte8nIzTdXezpeN5SzQhEky37CTfOASIocYUwvhHEOSbHtxTzUtId767g/SiukVVVPUnZ+97sLJ6QEFEjAGFZIuQ9Rn42Uri3msftW17H3aFuClRMsY2WeZ378Fu9+JLHfSiq+/e29E2o+VPD979eTqtqOG4JavBqngn4GyRJUk2eaBwJ8AIExChlkv/WDCM8+u9devv/9qvqLv6gnNfUVohYBc8bYKsXAFuiKHnJCWhTO+VTGAOB9e/xBjnCmzcSKQj0jhJjuI6Jrl24bmUWWGoeDfobIElTRBDKJpIA5N8HHvIsU0sUMGpJy9dVXZ/f23HPPXVshIBj3pscfr/bwvtp/+qeq2r69qgjyl19el899byPt0h/6Rf/oZ0giL/iBY0lCyocH7rjjjvol6yKXQ/LoHaTIoneFStdDZfvOW12rr6q/r5zOYWek448/PvuBC9U5pi1+iz+u9rDdj5BqUs0DedxqAh5c9dm4cb9ulCCkvbLs16IfWCQCEFD0xQddughpvSDDirqdiLNI07LKnktIh+LxIrGaUttOSKekrX2y4rgZjBqU7DdTvSr2ox9Ve845p3bg9SWv227jo/frshK03/nOd1YQnJRXX4TIsq7Bnh98zebss8+u/1K/PtVTffapU045pdL3xS2J4VaFkATBOO644+ov74SWadZLu9zn9va3v70655xzggkg95DWtsAl+698pXrh5z+vLrjgguqtb31rXR/1piT6cfDBB9crXSJQQ/VQBvKnrzRhd1deeWX9YvyQT2p21c+L+fmq0caNGyv2QxL57OQCoowMfHVMug6pp5mnTdexX2uSrg877LDq1VdfbTYx+d/4LXBilZSAvh8hZSJ1+eV7bzHBbv/n9+l5GG/Phg1VZb6kJJwOOuig+rahFGAGZYmoFPvm60Gy74iinjUQAZFQ9MYfv/dLfG0Ne+GBTt2qxKX7hm/AB2A7qb6nZAwkHp944okVn0BOicf7YTCxA05IJ6YwxNUAYB9nzoBspqEVUoydgAupYRDou9mxTjRElqZszd8iAVqh0ve+Y1Ygm3XO6rdwghQSCMFx6Hv2rN7wnXcus7MaGFKmTX7bNpgRzO134dvKNI81sVYwZ4Ug5rJys236Rf/6vmffLNPWdsp3xJttN/FuYsDvZhmONdu2eCNrSGq23aZr2XdfAExpO0S+MeXBb+E/uPWIFWn216WAFVI7oeB+VI3F0NVxtTcoizL2bGlT4xFZtCoeOjnqqdpPNRAQIeWSPbbTRkiHVkiZIMpn8WleYh8xKHaxoEQMLBWPGzBN7qcT0smprKrvm8GJk+TQ2SegrgU5OXNW737yk703dl9/fU2iIFOWgIgkEXRDnSiDGULLQG6TBSccssLUJAEEdK2OpjqIWau0jUiJ4ICfkvLh5NqCkspA4nBIW7duXcOSfYIaCSLHxKELT604gmVfamJt8zYdIjpFBhL70nGTcNk62BdBEGHXeXARIedYH+FqkuYuWdrIntpjKwK8Nib2nQQviAPnSX0EUTrUeEEnXCbkqy7sCyNk7hs7VtdgSJI+9Jtjytel67rgkvxDr3qQCUKhfcbD2njZd3tJ/ZaIhx6qV/nxZ8LJToCkT871jRcLH7aAHrpk4XamoXFlxw5tkyCn2M7QeLGy+H44AsQ9TWDQnfYZg2u+R/eQ8sDuvgfjuPXD+hdrMxwf8ilWQnSMfaBjZCB1xmNb0Ow3/QunsCHk4FyfTzHVLM2uE9IJqpKB05UU5Gonyv1WPMzE/YP33FM7eQLr2oDdVwmDkuNaHe1zonYwD90P10c6aBOi1iQLDEaOMxBjHUQXJrM6bgORVmQ4Rurre1Megi/9ZZWG2T5kRys2YEDQVf3Nsvrdp5c+wqXy2srJYj9atdJqBHlwwGtkQYUa2zYnK1yoP5QsaNKzbdu2VlnALGQ1Y92YqLgNca+OqP+SSy6p/zQJanRl7Sdl6Pujjz66tiJD8EFPJNrQ+Fkr1LIjwi77Rm8k6tfqnoJkS/GlOYSP4a8t7ed/uHR/ySX1Qyn/189+1okTvoSJhsZK3xgEY61mSgdtsvSNqzY7Vx2aTGusqL2mv1N+38Yh0KWz/XTCU/bXX7/3wbiHHlqbBNbx0TTJ/d52dZQ4xAS6bWLIWOW4ri6aavbbbfoemwHbyI3Htr5l2HdCOjEtMuAYOF0Dku5YJ4oj1ODSSlxbl6mXIEndXU60b3C11ckx6yCo1wabPhIghy7CoT60OYiutud13JKsH//4x8GEqykf5Gbz5s31qpsIaTPP0G9Lsp566qlgwtWsFxKKLNzbZwlpM1/fb+u4wSXUiTfrLCGLHROQSogBtj40qWrKIhIKLqyKiJA28/X9ZkzIvu+99961fdl6X9llOEf/CfYijl19apI4+Z8+nPATdsLT53/IG5rsuMKHdZEJW598HZMe+Tr1ga2nNATwK4zdvmR9D3rGlijTNyGgDJNCSzTtpAYf0ry62CeDzlnfUzIeq/5l2johnZg2GTB9Dtl2Byf43ve+tzr88MPXLk/a8237XU6Um75vueWWXiLcVp+OMdgZ6L/2a7+2Rnh1rmvb5SDoD7cKjC098MAD1emnnz4YaLvkFgmF7HBvsC5DdeXvO/7lL3+5OvDAA9cuJfXlbTsnEsolaWThd2qCeIAL+KSkkrIwJs4888zqW9/6VoootU7QE4Gl6/7t0Iqx70984hPVTTfdlDyuQtsaUz5WmlmRCk2Qt1j/A5GAgED8IaUp/qdNPiYwb3vb26rf+q3fWltpb8tnjzWvUEBQ8KWnnnqqzeb7gQhA8EMnkvgeHnTkgVRNCoaasQsM2I0mNW9605v2u7o4VJc9XzIe8+AmdrRsyQnphDTKIGQwxiRmdPzFJjlRHDqJSwuQ1ZxEECIYMcAJGKFJDgIyTmJ1BUKwbEmEFCKqy+WxfcRJsRIJzueff34yTiKB3D7Q9dBArGyp+ccki1ZI6Qv64s9TOAKQS1apYlOK/2EscNWHS/P4Lvmf2Lab+eV/WHmLWWXV6ii+FXnok6c4BFiMURwILRk7AVK9Wh3V5Ak/mJsUj7FNXYkMqXMW8Tik3XnnyUd43hKvaHsYMDN+ZmwxSQMgpozNq1llSkCw9bCvgJDqjCWLAkKz/qn/5iEZCCAJ4qP90H5B3Am+IvsE/tRLgzxgoodMkEv7obKUzDcmWdAJeJCQS/sl+7usdWGfjF0mpLEpx//gb2hT/ie27WZ++Z8U34ofx4en+sCmLKv0G8yIgbH2k0pIwZa2aJdUkpCyoIIdxSbFwJzxENvmPPM7IZ0n2hltpQ6qFKfZJmaJAaCAkOuMFRDa5FyGYwStLqcLAdKT3XYf4gkucp7gwAyc+4aXKcVOyGbZ9zHJMst+9tX96U9/ug7UBGtuycEG9cdKvfzPH/zBH9S3OKRiVtL/9PUn5Jz8j/oWUqaZJ9cHNutbhd/CPbavqbGz2c4YCKlkKjEeVNeYtk5Ix6SNDllSLtWrqhynqTrYlhgATkgtot37XJICq7ZkLxnbfchnk8TmBD0ujel2jTY5FnGMlV+CyxgS2LJas8pJt9IIA36z8qM/9CX/c+2112Zdoi7pfyRv6lbESH1LqSdnbKa0N/UyKZfq1WcnpEJi/FsnpCPREUvxOHKIhRwd94vygAtf5dm1a1eSpKorqbApVDIg5DpjBQQj3lLt9jlQSCgzde5dxDaG7mHk5vfYVSmILfqOLTdrJWhCM+t2QurPteGQNsacBxvh9hD8Fn9MmrsSK/4kVutj7puz9ZX0P7belH35nxzfuur204a7noa3ExmwZuX9He94x34T7rY62o71+dO2/F3HfIW0C5lyx52QlsMyqiYI5sknn7x2uYvVFgYfTluODicPSf3mN7+Z9CAAAqmuKOFaMpcMCLnOWAGhRcylONTnQCGkEFG2+gZ4X6dTSEDqgyd9cpQ454S0BIpl6pBfgZhCGPoe7uHSPb6MPJDYlFTS/6S0b8vI/wgDey50P9cHhrYz5nzbt2+v3vOe96zFQGwDbO2tHlpt560EqffD9/nTGHyckMaglZbXCWkabtmluBx6ww03DNbDgCSlEAvK5TjNuuF9/0oGhFxnrIBg5Vum/T4Hai/T2/2u/mNnPGkcmsa6Oor8TkhDtTjbfBBLSCi2EmJfloim+rGS/icXHfmfHN+a6wNz+zCG8tyadMcdd/SKgo1xKwhbcGc/NvX505i6nJDGoJWW1wlpGm5ZpWzQ5xIWzqkryflx2YsZZF/etjpynKatr2RAyHXGwsTKt0z7fQ7UPuVt97v6/78+9lh1P6+X4UXcAe+tG+vqKP1zQtql5fkeh4xCDLhUj0/Cnw0lEVFLTofK2PMl/Y+tN2Vf/ifHt+b6wBS5x1SG24HQKbbDuNZtHU0ZOY+NYWtgxn5X3mZZ/e7zp8oTsnVCGoJSXh4npHn4JZVWYLXEtKsiBi6X8xmErJbiDGNSqtOkXWawDGZSyYBAX2LeRUh+Vvn0DlYFhBgcppS3lAOlz/925ZW8r2Tv38D7aEPscZE4atwsUga1vaqEwq6IipgKk76tJaIip335m+dS/Q+3CojQlLIf+R8WE2LuiQUDyiLHqtqP9Kq4ZImpzjW34KYV+RQdpvpTdIStIiupJCGlbtXb7G/b71nE47Z2Fn3MCekCNICDZJCFDi6cHgODpIEcIjbluEfn2GOPjZpVskoGCdYXoZD1sMMOy37Ihf7yxQwGV2jiBndkIRBCmBjI3OC+ZcuW0Cpa8z3yyCPVBz7wgd5731oLzvigsP7Qhz4UvRreJtr/+8EPrhHS+w84oOIhJ4Iif7IlMGay88d//MdRE4W29mZ1DJvhq0YHH3xwLeus2gmpFzvE/t785jevvfM1pNzU8zD2GIv0P2UlXUTUEow+TGgP22Ty+qu/+qsVn1kNTZRlAssfq2ukz3/+89XHPvax0Co685111llR40RkAr+vW7Doy1ve8pYs/8NEHUy/8IUvBK1Sd3ZozifsxFc+aEgEa2+hBJN2sJ9DDjmkwp/yOyRpAQRb14QDvfGFrtzE55g/8pGPZMdjbId4mpPANLeOnPbbyjohbUNlhscsuRQxDWmO1UoRRM3Qm+U0ALkpnE/t4awuu+yy6sILL6xXODHAvsRqAoOQAMCg5I995PzpT3/aVzT4HJ+PZLUDR9TnILgkyKyYvuDQyUsZ5PvRj35Ur94iV+w9RQRD8AObxx57rO6b+hvciRlkbAYt7IS+sjKMHlLT/3LWWdX/fdxx1Z5zzqmqF16oscS58qdgAMZgwmdd//7v/z61qZmVYzICFti/1R+kY96JACf75cFEsMNOkWvZkwiVJaYxfQYj6iDdefXV1Ytnnsl9GPVvxrdsEhK5YcOGGmfwxW/x2cZNmzbVdiqC2dY29TBmsBf8GYl6aZdx/uqrr7YVizpGHfKL1N2XkF22Sz5rvw8//PCaXLFjnHqxw23btq35RZGnPnnGcA7ZwQ9d0Qd8X0jCLtAp5dBnmx2AIyQL/04MxH4ggMRB9DCEEeObfHYBhLrwjz//+c9DxBzMg87oNzj0pb54/Fd/9Vd1H5GrDYe+eu14iLW7vnpLnHNCWgLFiDowbgYFxsYAC012EDKA//qww6r/713vqv6fr3+9HoAMPJw4WwYV+UmaTWJ4XU6U+pALeWTccnhDgyZUfpsP2UQumw4COSHf9nKgJQHqF/Xh3C1ptW0099v6r8E4y7425Wj+pj+WcHGegM/xtnPN8n2/qVcPNLGP88IeRERxTPyJ2KEL7GAsSQ5ZpBx9KXghK4FD52Ytc9sESWOFcwRI7FbyzVqeRdT/3ve+tx5zjDv+UhL29XePPFL7Lt1KcssJJ9TkAfvENtG7xiZtsI9vI2Gv6B1fZvNwDpsg0LeRiVR560Y7/lEnMtMnjSFlbcqJrF3+N8b/UK/INXXKH9I+ciDPLPqqfpXYIj8yxr5blLFFWbYv/Pzn1T++853VniOOqP6PH/ygrov+Yyf4OBtXwER+rgsj5LGxBFy7YlQJDPrsgf4hZ0g8btpZn2xTsBEnpH0aLHwOo2dAkTA4O2hCmiIAUv7fnnhi7TIsTn3zVVetI6G2LowaB6+EDE0nCuGTLCIBbQ5fdZTatg0QBphWgpskoKvdLsKq/G0OH4cDliI0chAEO4uX6pjFVlhbGdhHLhvgcFBNkj4kD9ihZwUs6gBbVg9ESDnPn52t038RraE2ZnWe9rFb65CxiaZu6JvIPDYwiwRuBDg7QWKsIAtt2yQZRYjsuWXYp9/4rZzEOHv5xRerPW9+85oP2/Wd7/RWiT2At01tYxq7Rl/YBeOIMvJrtmzpfdkDbWq8IZ/GUZusTRmG/E+br6QO+RD5LMY4/gN/QZ1jS9aGkJN4FJPoHz6ruueeNfv5t1/5leoPbrqpU9fYgXRBW20Y4RfxmaSheBIj71DeUvG4z8bmPR6G+tx33glpHzqFz+EkCFqWmMY2wYD+P3fsWBuMew46iA/udlbTHIzKaJ1oHST2zbAtCVDeWW+tgyCg8BdLwBh0BCTIlciJnHUXuaaMCI1IsMgQgdeSwpIYqA2wVhshZCaUoNMv9K66Y2THsYHXIhJ2KCLRFmCxi7bEca4MWNLYli/mmLUN3WfVFjyadaoPBFv1oZlnyr9TSERbf79x6ql7byW5+eZe/0XZNRLSqAissVVsXViLTMx7UiB7ifE/je7UP+Ub5H9kT/QRn92WVMb6bvyJnWi2lVvEMWREV5aYxsqBju2izB7eItKTuHSPfpqpiVGof23WU+J3iXg8pvGQiokT0lTkIsvx3XEeKGFgQJxEgCKrWcvOZa7//aqrqmrgvWxcwsBQ25Kc6NFHH12deOKJnQ6vrewsjoHJ8ccfX/+l4iNywoNP1kH3ySsCTLDVLBkHccIJJ1S33357X9Hoc/fdd1/1rne9ay2ANsl4SIU45MMPP7x68cUXW7PrNo3WkwMHsQkCWRf5GyiefBobZXxo1bFrRaivAXSHHX//+9/vyxZ07phjjllbPbf2gb5CEiTh7LPPrh+kCck/lTw5REJ9ZGwz4QxNTAiw6a4E1hdddFH9RTsmJvO2XSsXbSMD9hPqf2x57YPzcccdVz+QE0quIXoQVyZ1jCcRlCOPPLKVkKmteW2feuqp+qFW2kOfmkSktI+fuvXww6v/cd119b3xXXWAgW73aMsjjI444oiiE9q2toaOlYrHGg9vfOMbq3//7//9QsfDUJ+b552QNhGZ0W8MX091Y3g5qWvFoFkn7TA7HEqQ5VyZhtoIPc8DAyUePNArOhicoX1jBYxVNpwlZXgSlm9wl0wKrtRP4OLyE+2GJq3WUa6NHKn+0Pra8rHqxErpPBMEFCJM0qo1QTk0kZcxptsRQst15ZP9gCdBPmaChF7oTwlddMm3yOM5q6QQNvQcOibpJ/YAyepL4M3EeiwJn5qb8D9X8tq2fffLh9an8aMrRRBb8Fl04iFAJozYQIz+2+QOHVv4f8bvUCqhr6E2Qs+XiMfo+9BDD113W1po+4vM54R0jugzOHDmuYNx6P5TDJqXphOgcWjsr1oSoegibn144MjBLtTp9dXVPGfrjCGiqqevXzghnG+ufaWQBsmXukV2EdKYSYTak55LE1LkwhZiklaora5jyo89b84qqS7ZhvSRL5GRwPF73/tebxFrP70ZJ3RS9pPSN8awCCnjijrGkEIXU4ZkHZoUKQbiS37/939/5WKgbIZYoAkK9jT25IR0zhqKvVzVFC9kxnfFFVfU3zqnrN1v1rXMv/uIW2i/FRBC84fky62zr1+/8Ru/Ud92QTCKWdFrk5vVWwW0tvOlj8mBptY7K0KaIs+yE1IwESFQwNNEQFtsB/JhV/FjbV+2Tnt2v00nufbTVueijwmv3L6NiZCCKavdkKTUxKV+JjZ9ycY9u99XZpnONW2GmIBfKnmf/SzwckI6C1QH6hxa4ewrHnI5lQH44IMP1qT0vPPOWyOnffUu2zkFMBGVlP4pIKSU7SqTW2dfvyABEElIAkEIJ5SaWL2FdMwrNR1obLvSswhRbPlmfuHcPB7yexUIqV0lxaaFu7a6HQW9oFtskdX7mNVmdMAqKX9D+si1nxC9zjuPfEVu38ZGSPFP2IXu14/FNSR+rnoM7LIZPbjFPdw58SFWZ6H5nZCGIlUwH04Z59xnEBACVhcgGcwmGcTkx7mw35cYjBBRtnLqffmX8ZwCmIhKSh8VEFLKdpXJrbOvX5aIpj4tD9HQU/Y81LV9+/aurhQ93uVAQxuRnkWIQst15RPOXef7jq8CIaX/J510UnXDDTfUq/JaDdW26dtSVtzRAT5MfqwP81z76at7UefkK3L7NjZCCp70aej2IsgT9gQOuqc9dKK86jFwyGa4ggb+OQ+WzWJcOCGdBaoBdTLQCKIknDeXIPiNE+aP1Sl+48hFSENJBoNR91/Z/QCxliaLCIWISkrHFBBSynaVya1zqF+ykdDJi5UTJ4bdMWGyK2A2z6z2hxzoULvSsxPSIaTKnYeQXn311WsvZEcH+uONCfJlbC+++OLohmXrFLT7bRXl2k9bnYs+Jl+R27cxElKwVf/Y51Y0bIdLyrIb9jnGBE+ENOQKIfXZuGf3F63TebUfYjP4+ebEcV7ydbXjhLQLmTkct8FTKwvNZln14tzTTz9dv0okxIC2bt1a6alBu9+se5l/K4Dh0MAvJVmHmVK+rUxunUP9skQ01HkjJ3YGVqxK4MxETNv6MItjIQ60r13p2Y6pvvxD54TzUL6286uwQqqJT1v/Sx2DSCjZfR2zW4IrNrBMSb4id2yMlZCiK40Vxbm2y/joFh/Op56PPfbYwSuE1Gvjnt1fJvvo60uuzfTVPctzTkhnie5A3SIBX/3qV9fuwdJKKU6EoMhrm3C0XIK/9dZbB2r000JAhEJERcdjtgoIMWWG8ubWGdIvEdHQy1vIbB80yMFsqP9d53MdqGR2QtqFcLnj6Grocmu51vpr0v2lu3fvrq8KDRHX/trGdVa+IndsjJmQQjZPP/306rvf/e5aDGQs86dVdt4jym9WTMnnaRiBXJsZbmE2OZyQzgbX4Fr/6I/+qF75VCDlng5mgxiUp3QERNy4AR5iFppYYWTWziUkBYTQsiH5bJ042dinTekPibJdK7/2TQwhDwBQD/WRZIf1jzn+sw4UQs1N9wSr0EQZ6iglv+yHlUAwjBmP6JSVHqvr0H5MIV/Mq5tm3R8R0s2bNy8tIcUnQcZiErfc6N2tYyak9GnTpk31C/M1dvFH/IVcDYzBZJXyWn86pX47IV2gtlghxVn4wCuvBAhFDK7oAoeIPvS6I1auL7300qLC/fCHP6zOPPPMmmxBuAgasTeX0y/k/Kd/+qdO2UREcezch9yVqIvL82wtMe3KP6vjtM9KCGSaxE339FH3joW0iw65V/GWW24Jyd6bhysTunxIcEdH6CqGJN94441J9072Crbgk7Mg2V/72td6bbmvyxBSVkX5u+uuu+ptX/6hc3fffXf1ox/9aCjbXM5v27atuuCCC6LaYvLN5JLxz5hiTBx22GGdX3WLqnwGmZGRcY6cnsoh4IS0HJYrU9O8HxxZGWCrqvrOd75Tkwg9ENbXdwgoThFCimPESbJK+qEPfWgmT5nTDgRH7wqFhLHqxJ8IWZu8yEZ/KEvg7EuWXPY5ewgfeSFaENOYlcC+9lPOPfroo3XfWO1EHv7YDyHsIo2slMWQxi45IfusSkHmFdiFvfTWVRYiC5as8vJ1mmVJ4IAuSuALJuAExkz6+MwqY442YpIIKffMMwlNvWSvMQgBvPDCCwfHYoyMqXmxHVYPwUiTo666wA17w+4YzySutvGbNyGMNc3jXuSx9n3WcsVcGZy1LKH1+wppKFIzyIezmKLRzACKmVRJ4GRVC5zbXm+hgNhGOlgJmmXqCiAEfEhYk0SKcMWs0vE9bYKZLoVBvAlWbTanFdVZ9jm0boIUOIj4iSxA2JuE2a4INc+FtteXr22yosDfxBGdYktg3jzX18ZUztE3XT3IkRmcIJ9NosWYQ+8hk0jaZ/yKkPKbyYgIKbYgxsFFnQAAIABJREFUYtYnq3wE7VofITIXM9762sk5Jz+F3YGdTXaS2jZe+ia4tp5F7CM7CwHNPi1CFm9zHAg4IV2QHuRkFtT8SjVrCY0cNM6QoIgeSCmErwSIllDJMUPIJCdbXYKLJVysGhGURUghFNQFQWc1iT9IAQ8VXHfddSW6U6wOsBDxE7GAJKAnEkSieb5Y442KsBUwJHiqffSmSYs9X4KwNZqf6c8vfvGLdd8gM+Bs/+iXEv1m0pKTqE+rzMKO+tjXpNASRGHdbFPjGXmsjDYfYwVbV732nPbpswiwjtF/Xamw8orsKd8itlZe9Rt7E2kGu9ArCouQv9kmsqMfT46AEHBCKiTmvB3TitScu76w5iA0BCBdEkYQG9xiCV/JjhB87W0DNriIkJVsT3VByHmdylhTF2EHq3mTBEgy4xaioxXQpt7GimObXJBDLk9DtiH39Mv+cR+tJi7s59x+AE6MPZGnpjyQE5FDyBZjEaxFDslvx4RdzWzWZX9Trx1XnGM8MSlrW3HkfHN1tG1yZNuY534XYRdZZTI7leRXCKeiqfnJ6YR0flivtYSzxUl6WgwCOG3wv+yyy+ogGBrcZi0tgRhywOtOjj766KgHemYt26Lrh9DwDsKjjjpq3YRiEXJBaH7jN36jeu9737v28Mgi5Mhpk4kYhACbY5+/vsQkLoXs8KUvVuEhl0MTPpEt5NKYZAtR/chHPlKP2RQZNK5OPPHE6sMf/vC6CUVXnymj1VxILUmTo09+8pPF7qPtan/ouAg797lzhaOLXA/Vs6jzjCEmP54cAYuAE1KLxpz2U537nMRbiWYU/MbYWS61v/rqq2MUbaEyQRJ27NixUBls488884z9Oal9yIBW3rlsCunTaihbvf+YfKyis0rIJA4dxKQvfelL1ec+97m6SGhZXbVgdZR2SQcffHC1c+fOmKb3y/vNb36zfniKE6Gy0D74QKpF2pmM8KGSMaT77ruv+tnPfjYGUaJk8CuEUXCtTGYnpHNWNUSIFbBQhzhn8bw5R8ARWHIEuLzLilpfwj9BWPmTr0qZSOv+ZVYXIZgxidVRVilJkOGhFdahurlXlfvGSfjgmAQp53YDkiXzMXV43r0IQOyZAHlyBJoIOCFtIpL5G8eFE8f54YxxYjgw/njPIqsPJ598cmYrXtwRcAQcgXgEIHWQAZHMmBpSVklFSPGJ+MDUVJqQ4odTkxPSfuQ0kWHig/6ZyCgG6r7kD37wg/2V+NmVRCB9VK4kXN2d5otLODku7TD4mIkzGJnha4CyOkriEpDuS+qu0c84Ao6AI1AWAVYpdX9mSs3cwwnBCE1OSEORmn4+FmGIgSKfrMKjf2xGMZAH45hc8N5ZFm88OQIWASekFo3EfVYbGGS634lqIJ8ahJBSBiZElMsVnOPG/dxLUIniejFHwBFYQQTsJevU7rf5ur66nJD2obN654iFXDUk9hEDtUizekh4j9sQcELahkrkMXtPFrNDZolcntdMkQGIY2ZVVJfKmB1yXr8jm/TsjoAj4AgEI8BkmUv1JQhAzCqpE9JgFS19xuZkhjdn8HCTJ0dACDghFRIZW2Z6ei9hTDUxjj2mXs/rCDgCjoBFgE9i4m8gBUMPNNlybftNYtGWR8eckAoJ37at0Kc8KOdILi8CTkgzdZs7y2OVlEv7nhwBR8ARmBUCTJiZOJNSX7nDKquelL/xxhsr/oaSE9IhhFbnfNvCDZMbjuuVWquDhve0DQEnpG2oRBzLfUgAJ8+AtPefRjTvWR0BR8ARCEJARNSS06CC+zLJ18Vc/hch1S1KMe0hJ6tqpNJP2fO0d0zinkdWmEm+iBCD3N68PEinyUyzNGSUGAg59bTaCDghzdB/qmNvNskKKU7OkyPgCDgCs0LA+iuR09C2uP+dhzJJMWW3bNlS8XJ8Uuikm/tcuZRrV9R4b2juQ6D33ntvdcUVV0TJAkmCVHP/ra5kfeADH6iefPLJup6cf0899VRO8UmVHbKZtsv5k+qgC1sEASekGTDyaifN4FOr4ZI/6corr6xuv/321Gq8nCPgCDgCgwiIGFhyOlTIXsWxxHSoHOcffvjhenWTBztDHqhiFZLVUK1GsnrGyhqfjIXc5iQ+Y8rnXkM/s0lfkQVCCjEFB8pCjvkMKQ+zpiRWC0855ZTq1FNPrfu27JerQ22NCY+/CirFopanjBPSRF3inHBWOZcZ7P2ndjUgUSQv5gg4Ao5ALwKWHIic9hYw7022xHSojD2Pj+R1P6wydpE4Vh/xgayMQly1SkoZvTdVl/9t3Sn7yEC9yNTmv8GIK1YQJPrcJr/IKTJr5XRIFpFrCLZIKH1DFvV7qI4pnkdvXXqfYn9c5tkh4IQ0Edurr7662rx5c10axx4y+282xUv0mRH23V/TLOO/HQFHwBHIQUBXdiw57arPTppVrivv0PEuEsdVJggg8pAgL3aV1NZbipTir1m1hQzqKhXtiBiLZHKOPF0rvCKvxAD615bayDX5WG3VbQhaGV5G4tZG+ttw8mOOgBPSRBvYuXNnPaPH2VinHVqdDQahKxWhdXs+R8ARcAS6EIA46eoORKuLSFEeMsb5kpNmS+JEyGhLZBCi1jfBL0VKaZP28b+WEHO8S0bOtSVigL28rzwimroFQcfZanVUZJc+0/eYVVdbn+87AlNHwAlphgbtjdixqwcioZaYZojiRR0BR8ARCEYg9P2PkCRWuCCmljwGN9STUauPt956aysp7Cla39cJMQ1JEF1I32mnndZJdEWGb7jhhuqmm25KIoXghEwQU+53BbOhS/H2dgDuWSWJDG/atKniU5ueHIFVQcAJaaamRURxLMxsdW9QX7V2hSI0MPTV5+ccAUfAEYhBAB/0jne8Y90X5Vgl5I/JslYh2X7sYx+b2T2A+M3rrrsu6eFQydjsNz6YFUnu1eT1TvSJ+0UhwOz3rb7+0R/9Ud33Zp0xv8H2wAMPDIoFqpcy3LOq27g4DlG/9NJLlcW3jsDSI+CENFPFOFStHuAIIaUc60sioZaY9uX3c46AI+AIzAIByBmrg/YP4iayx/bzn//8LJouUify8XYSXa3iCXitTHJJXL5YK71afewjpSUE4/PRJC7BhyxSqE2eKYCUshqtPumcbx2BZUfACWkBDeulzzi/ISdCHi7p4BCZtXMpyZMj4Ag4Ao5AGgKQ0Isvvrj2vUzy2xKEm5Vf/O88SKkIKSuytJ2ShmJJSp1exhEYMwJOSAtph0tErHyScHx991vhNEVMuxxoIbG8GkfAEXAElhYB/OiGDRtqf9rncwGAFdN5kVInpEtrct6xGSLghLQguH2zYZylLotxmemyyy6rrrrqqoKte1WOgCPgCKwWAvhU/C4JYjp0KX5epNQJ6WrZofe2DAJOSMvgWNfCaidfAuEdpThJ/nBM/HGZXscgpHxOz5+gLAi+V+UIOAIrh4Dux495W8k8SKkT0pUzRe9wAQSckBYA0VbBAwF8M1mrofac7zsCjoAj4AiUQ4CHSCGjsffjN0kpr4QquUDghLScjr2m1UHACenq6Np76gg4Ao7A0iDA5Xku05O4+hT78BCkVA+VHnPMMb33/ceC5oQ0FjHP7whUlRNStwJHwBFwBByBySHAi+R5d6d9sCmlE9zfzy1VJVMOIWXFlz75U/YlNeJ1TQEBJ6RT0JLL6Ag4Ao6AI7AOAX2UhJVOXoKfmmZB/ERIWbUdetBKcvMMgl6OT5lZyKW2fOsIjBEBJ6Rj1IrL5Ag4Ao6AI9CLAKuarG7qwabezD0nIYH6bGdPtqhTvBsVuULIKKuhPOhKfyQHq6RnnXVW/RWrqIY9syMwYQSckE5YeS66I+AIOAKriMCLL75YHXvssXXXIX5D7yDtwyjkdVF95bvO8W5qSCbbrsRDsOSBkEJMWSXl6048rBV7T2xXG37cEZgKAk5Ip6Ipl9MRcAQcAUegRmD79u01acsholQU87qoFOhZIYUw8zlTbi1QgnzyIBYv6tfHUXhTAPnuueceZfOtI7BSCDghXSl1e2cdAUfAEVgOBCCjkLocUmq/sDdLVPiePfe58qdv22sLUYWI8sR/yCX+WcrpdTsCi0TACeki0fe2HQFHwBFwBJIRiCWlemepViFTXheVLOy+z5dCPlk13bFjx34kNaduL+sITB0BJ6RT16DL7wg4Ao7ACiPQR0o5B/nkwSXuFeXeTFYiWZ3ksjnH2M47bdu2rb531F7Gn7cM3p4jMDYEnJCOTSMujyPgCDgCjkAUAk1S+uyzz9aEjweGeEiIp9d1OZx7Nnml0qWXXlqdfvrpUe14ZkfAEZgdAk5IZ4et1+wIOAKOgCMwJwQsKWXVk98k9lmJ1MNFvJJJ7zB99dVX5ySdN+MIOAJDCDghHULIzzsCjoAj4AhMAgGR0qeeeqr+vj33iB500EH1vZo8wKQHiSbRGRfSEVgxBJyQrpjCvbuOgCPgCCwzAryjVE+t+7s8l1nT3rdlQ8AJ6bJp1PvjCDgCjoAj4Ag4Ao7AxBBwQjoxhbm4joAj4Ag4Ao6AI+AILBsCTkiXTaPeH0fAEXAEHAFHwBFwBCaGgBPSiSnMxXUEHAFHwBFwBBwBR2DZEHBCumwa9f44Ao6AI+AIOAKOgCMwMQSckE5MYS6uI+AIOAKOgCPgCDgCy4aAE9Jl06j3xxFwBBwBR8ARcAQcgYkh4IR0YgpzcR0BR8ARcAQcAUfAEVg2BJyQLptGvT+TR2DHjh3Vrl27RtGPl156qdq5c+coZOEzj9u3bx+FLAjB14A8OQKOgCPgCJRBwAlpGRznXssrr7xSXX755dUhhxxSPfTQQ3Nv3zb4i1/8ovrKV75Svetd76o/12fP+X44AsLxhBNOqE488cQaS77DvYhEu9/+9rerd7/73fUf+kW+RaV77rmnxgRsbr755gr7X1Tiu+innHJKdeqpp9afpPTPUaZrAiyPPvro6mMf+9jCP+v57LPPVieffHJ1+umnV+x7cgQcgfki4IR0vnhntyaiwKfxIKIE5muuuaY655xzqueffz67/tgK7r///vozfZAXVrAgLshGoPEUjgCEC9zAER2LnHLs8ccfD6+oQE7ao12RUGtzyDnPxKcfzzjjjHUktInVvOSBeF5yySXrSCh2Dla33XbbQgn7vDAo1U4TS3BEz7K5Uu2E1GN9KESUP/zp9ddfv9CJT4jsnscRWCYElpqQPvHEE8ukq5qYNImCvtWME20G7ll2vs1pS5ZmsJmlHFOvu0m4IH9f//rXq5dffrnuGltWwj/60Y/OfMKB3miH9tQ+ekYe5CJwszqJnUnXs8Kftpr9RiYRv3kSdtqiXcaeJlr0n8mD0p133lmvJM+bsKv9qWylN2xIWDKRRt/znvjY9nSVCRtjHJDsZJu8nhwBR2C2CIyCkEIc77rrrmr37t31ln39cQ9bnXbvrqq77nr9r/H7uX/8x7rMc889t4YYdSxDaiMK9Avn3lyxmfXqUXM1weJL0LZkRatHi1j1sHKNcb+NaBIUuUQOAWymJnFtns/5bQlXk2gSiJEHuRS0IRBN4prTvi1r22tbGRbxY0tqw9HWl7vf156Ii9oAx3kRdrU5pW2Xb8LmZPfo3058mBDNIjWvAqgNbNuueItAc6zNHlXOt46AI5CPwCgI6RVXXFHxByFle8ABB9TkUvv1Sufu3dWeK66oqgMO2EtK+b15c/2bLYSU/JbY6rclqfmQza+GPqJgpRDxm+XqkSUKIiZWBu23kRVWknDovnq0dxKh1TYFODDjEiG3XhCM+5KC+je/+c2+bMHnvvvd79ZkQASvq2DbRERB/dZbb+0qFnWcFSlLTLoK23GhVTYR9htuuKHIpfPHHnssmZhoDGzatGk0D6d1YTmP49JN372/bf4lZlyE9kO6sVcB2sr2TUSow5Mj4AiUR2A0hFSrmWwhpEoipZDVeoXUnKtYDeX3vlVRyqoeytt91Tel7WGHHVYNEQXbnzYnetZZZ1Vbtmyx2ZL23/Oe99T1EDhCksiKvdx76aWXVpdddllI8aXN861vfav6zd/8zf0ugcesBEHIeLjnpz/9aRZOlIcAUl9o0q0aIs/Yw9lnn5092YDwbtiwYZCQWzlZoWxeIfj0pz9dffnLX7bZkvbf8IY3rF261SRA9/eGVghRx+ZXOeF7mIyGkjg78VEZJsA8vBljp22YU8/GjRuDbzexEx9dOWB71FFHVbwJw5Mj4AiUReB15le23qjatJJJoSYh1e96lZNL8FohveuutRXSLkIaJcQIM4uYs3IU6oytE8W5QwjbLgHHdhfiwuVRiCbbkGRXPSAP9IMHBVY5WQxYFY1dNeZSOYmtgmQqnpS39cXUQ3BHfhI6pV85CZvCxkisXoXaO/lZJUUWypSyd4096utb2WvrM2XA1uq6Ld8qHJM+0E2MjTDx4fYfTcjlf3Iws/pQvSH16ZYprmyQSoy9kHY9jyOwagg4IR2xxhUUUxygSKMCQm43FRBSyAfEGHJqA0KuPFMtn4tBjk00MbOEVPU284T8TrGJZr2WkMrWmnlCfpey9xJ45Oo6pL9jzyN9WFuLkVl+LMcm1J7VR4p+JUuKP5YMvnUEHIFuBEZPSDdv3lxfwk+5ZN/d7WmckdPMcYAKCLk9VkDIIR82IOTKM9XyuRiUsAlhZ0mC6tW5mG2OTagdJ6RCYrm28j/W1lJ6KP+TUlZl7NjLsfccfyxZfOsIOAL7IzAqQmofatq6dWslMhryUFNlntDfv5vTPCKnmeMAFRByEVBAyCEfNiDkyjPV8rkYlLAJYWdJgurVuZhtjk2oHSekQmK5tvI/1tZSeij/k1JWZezYy7H3HH8sWXzrCDgC+yMwOkLKPaP6e/DBB+sn72ux9VCTXv3U8lvl9u/mNI/IaeY4QAWEXAQUEHLIhw0IufJMtXwuBiVsQthZkqB6dS5mm2MTascJqZBYrq38j7W1lB7K/6SUVRk79nLsPccfSxbflkEAu4q5H7hMq+21cK8xrzj0lI7AaAgpDzbVl+UT+8JDT/bhqMRqRlVMTjPHASog5HZMASGHfNiAkCvPVMvnYlDCJoSdJQmqV+ditjk2oXackAqJ5drK/1hbS+mh/E9KWZWxYy/H3nP8sWTxbRkErE7L1JheS66Np7e8PCVHQUjti/FToYWQskI61XeOtvVbTjPHASogtNUfc0wBIYd8jMl5xPS9ZN5cDErYhPpjHajq1bmYbY5NqB0npEJiubbyP9bWUnoo/5NSVmXs2Mux9xx/LFl8WwYBq9MyNabXkmvj6S0vT8lRENLlgbNsT+Q0cxygAkKuZAoIOeRjTM4jF4/U8hYDHFhsKmETatM6UNWrcyFbvTs1xybUTi4hlSyl7F14cBmOt0TEJOFhdR1TfpnySh/W1lL6J/+TUlZlrD6kX52L2eb445h2PO8wAlanw7lnmyPXxmcr3TRqd0I6Yj3JaeLUCdihSS/yLvleRgUE6lbwD5GHd0TyPkF/D+letKwDbX5qNQRPfd2pRFC0DlT1hsiA/nnvJ+/nJImAhZTtymMJKTYT+gEG7IqX4/PuUr33lvGSmzT2kIUXu8e8FB9c9d5NsFnlJEKKfmP0wiQA+xJ+8j85WNqxp3pD6kOX3BuInZFKjL2Qdj3PMAJWp8O5Z5vD+tPZtrS8tTshHbFu3/72t9cv/Q4VkQEB+dOLvHGkF154YfXFL34xtIrOfHydJOYl7iIKOHH2IQu/93u/V33qU5/qbGMVTjz88MP112JEAEM/ZWixQQ9vfetbq49//ONRExVbBwSB8gcddFDwQwGQBL7QBBnVpIR+8PUb+pWTXn311erwww+vSUsIGcW29QlWSCMJ+z/yyCPrP/ZTksjHm9/85rp+futYzPfM0StfSbvuuutSxFiaMviec889N3iVGd03PzWMrWEbu3btysKFW7pOOeWUqDGjyb0mJIybY445pvrZz36WJYsXHkYAW2DiIF/TVmKIkGpiQwzKTcRV+Zq2uoYIqfxIqm9qa3PZjjkhHbFGLanDEXYlzrFCxMxdn9uzjrSrXMzxNjLSVp5B1yQKWmVilSGEbLTVu0zH2vQFsYPwsIrUhRGOzE44VAZcwT0kySmKXLXpq1kP8iAXq1R8oYmUQqSb9TZ/t7XTzMPvtk/kWvtPlc2OGWQZaqdNNgVA9OSBZy9CTVzbcONY057BEkJiJ0BdZUOPN9voKtcca3bc9JGSrvr8eBoCuhqDHWAPzdRFSBm/mtiQp0QaisfYDDG4Ldkx0Hbej+1FwAnpBCzBErom8YCMiFzQFQ1grZKW7p7qb3MQDDpIi17DMTSAS8s2tfqaQc8SMjujbyOw6qt1vOBPYiXotddeW9tXXusUKWeT1ZVtm310KqI8D8JFG82VWGTlOLbOhIdxYEkCRKOZmuSDhydfeumlOhv7eqtHUw+2HtpoTrCUX3au/AqA0oOO+7Za0xVEvUnosG8COZMK9q1NlyITVge2fk2wdB5928kNx8mD3WmVVHl9Oz8EsIM2HbQRUuwLO4uZqMf0pCsetxFSxctZxeMYuaeQ1wnpFLRUVeuctJwozpPgh4PtCuKz6l7TQSADARqZ+MMZtAWfWckz5XqbRBFdgqdwtBOOrn5SBqcHCeP+Rz4qQdK9kBwPcYpNZy7bYjtvwtXmzCEspCZm9cGWf5IbQs1r4U466aQ6F/u8kQPcuK1EVxZaqqgPtRF2ydIVoLrqWuXjbTgSyPkjNe1vlli1+UzsQJMb2R+TI/J6WiwC8oc2rlhC2mZbs5JYfgXfrHhsCWmbbc1KlmWq1wnpxLRpDR3nqYFhL6fOq0tdDqJtJjsvmabajrAU+QwlXG39hYRCuFgNFCFty9d1TDaFLMjRXGnsKjer4xaLp59+et1tCzFtggl/fHBDhDSmPHlFPlk13bFjR01mdZ90bF2rnF84ahULcg+Oi8BSxFNXffCxpW8VWGVdl+67JZ7btm2rrr322noBBH+FXc0z2Xh83333Veeff349cV9EPJ5nv2fVlhPSWSE743pxou9///urd77znfVghEQsKuEgLrroooqHsOTUFyXL1NslMP/mb/5mddVVVyWvykBC9aGIFEIqDHG2H/rQh6rjjz8+6kEQlS+5hbBDIg899NDB1cyudinPKgarpOedd17WO4sJhASdeQfArr5N9Tir7occckh13HHHLRxLVtuOOOKI+o99T+NGgLGHP+ABROxokYl4jD944xvfuPB4vEgcctt2QpqL4ALLE1w//OEPL1CC15uGSB199NGvH/C9hSEgEsple+2nCsOlbv7GkOzluRR5tCrK/aMi7Sn1eJmyCFx55ZXVvffeW7bSxNpuv/32ij9P00AAu9m0adMohCUe82YNT+kIOCFNx27hJe09K4sWBkLKDNHT4hHgoSYSD+1oP1WqZSKk9kEmcNFDTanYeLkyCHBVZSwrkmOy9zLoLnctuZPUkuiMKR6X7Nc863JCOk+0C7c1pgHghLSwcgtUx2Xu3DSmAF0q+JTAJRdXL/86Ak5IX8fC9+IQKOUT4lptzz2meNwu4fiPOiEdv446JRzTAHBC2qmmhZ3YsGFDdtvLSEh5cIZ7vjyNAwEnpOPQwxSlcEI6Ra11y+yEtBub0Z9xQjp6FS1UwNz7RxF+GQmpf/pxoWa5X+NOSPeDxA8EIuCENBCoiWRzQjoRRbWJ6YS0DRU/JgSckAqJ9VsnpOvxWPQvJ6SL1sB023dCOl3dtUnuhLQNlYkcc0I6EUUtSMwcQspro3jwh/dE/qf/9J/Wvvy0iK5Ilm984xv1V5P0FapUWZyQpiI3m3JOSGeD6yrU6oR0ubTshHTC+nRCOmHlzUH0HEIKGeU1SWx5Zycvk19UKi2LE9JFabK9XSek7bj40WEEnJAOYzSlHE5Ip6SthqxOSBuA+M91CJQkpNjaolKTkObK4oR0UZpsb9cJaTsufnQYASekwxhNKYcT0ilpqyHrn/3Zn1VHHXVU/fnQxqm5//znf/7n6m1ve1v9/fW5Nz6SBsf09R6+r/ymN71p7TvLsRBZEnjjjTdWW7duja1iLT9fVHnPe95T3XnnnWvHYnZKysLT9XxR7Oabb174uOHNFLlf5YrBcax5Tz/99FofY5Dv4osvrvjzNA0EGMfYzxjSmOLxGPBIkcEJaQpqCy7DJx0ZiGeccUb1mc98ptL3zxchFp8s5UlsXooPcWGbSjwWIX+JNiFc6GAM3zeHcJ1zzjnVNddcU+3cubPe8jv2NUdNEohuY5P95jTffQeflO9Nl5DFfnP6pz/96ZrNQtznnXgPKvfmatzec8899T6fP1zkJ4DnjQMr3fgwvtTEbSGXX375wj5R+/zzz1esnPMJZP7Y55incSLAZA57wW6wH+wo98pJak/HFI9T+zCWck5Ix6KJADkIVgQtAhlBTEmDc95OlGAOAYWQKpASbFOJh/ozla0lXOyT0AVJJBXiMY8XseMUufRpyadksiSVfH0JubExPUgEGeT+UT1IRP1DJM4SLuojSZY2zLrkQW4mXl2yEJCGJj8aM9ip5EZHHLckNZawd8k8dLxJPpEBWYQZgVWYDdU11fNd/urxxx+vfdu8xgz4gb8m95bQiCxzbmjMTFUPU5Rb40STOfVBE4p5TmrkW8YSj4XFlLdOSCeiPYIUwUrOmoEJ8YMMKs3LiTYJjgYm8ihZ4iGSpnNT3wp7HJHIg7BvEqS2CUTJ/gt7ZOF+KptYJbWTlLYJhPJbffUFYM5RryW+qoOtJVz2OHZrVzHADZmxGfC0aagN5W3Tg86xtQQHnJTQEW1zntS0Z+UruZV9iOAgj64siKzTntWDPV5SlkXVhb6wgzbs5SOsPWsCMQt5bTua3At7dKVk7dnakM77dn4IYA/Yjq4kyE9Yv2fHfNOvlJR0TPG4ZL8WXZcT0kVrYKB9OUm+LqMARUDtuzQ+KycqB2DJyJADEPGA0NztAAAgAElEQVQQkR7o7uhPN7HvWu2xHQG3tlUYmydlfwh76uwjQjj4IVLXJVeTxDXbaSvXtoph8bQkLYaMNMdIWztNedr0RpvNFf9mudjfqe1o3LQR9lgZxpC/6ZPafImVc+i8zRu73xw3Q2OgjUjHtun50xFo+pohP9E22UhvfX3Jpq/hrPVh63Pv/dW0/bY8fmwvAk5IR2wJ3BvDjJDgRFLQDwlScqInnnhi9fDDD2f38vOf/3wdrEUUQoK+GpWDOOmkk6rvfve7Ojy57caNG9dW9ISvXe0Z6hCYnXXWWdV11103lHXw/AUXXFDf66aVpaECTadIwGeSc9BBBw1e9u6rG3v4tV/7terUU08NvueujRB87nOfq371V3913e0ffe22nWOcHHbYYdWRRx4ZfD+ZxlRz5fLoo49uayLqGOMOm6G/pGZgDamMYEd/Xn311ZDso8uzffv26pRTTqknZNjcEJlodkCYlXjQaNeuXfUqvb2sq3EBzkNJkwtW+qnL02wRwMd+8pOfXHc1Rr7D3ibWJQX2xrjG/rDD3DSmeJzbl7GWd0I6Vs1UVaXX9jCwcKL28uuQ2Axm0pe+9KX6byj/0HkC64svvlivqMWu9kmWH/zgB/W7LYfaGut56UOrV7p0FCIvxAccSr2mBFugTkhuKCmlfV0ypRzlqSc36bU9yEG9IUmTFE24CBhveMMbQor25iFQ8Udf6V9oEjHR5T/pOrR8Wz7pmr427+9ty988JiLLqm2ojpt1LPr3li1bqi984Qu1GCkr0PIdkPJcDO69997q05/+dC0LRBdiqYlICE6ShUnl008/HVLE82QggL6POOKIugZWJvFVdjIxVLX0demll1Z33333UPbB8/IJY4jHg8JONIMT0hErTgOAYKngFCouq184XQXo0HJd+RQUkQN5YhJOn2CkAB1Tdkx5pQ+cI04pJom0lcJAhDRFvzh6/koT0pS+gSN4liakKX0jgIlQS9cxOm7mtXjoKkczT9dv9MOYI2nsdeUd83HZJ9jGkD/6hG0wYSGVwMDqg4mZdB2K34YNG+qsGnuh5TxfGgJ2DDD5j5lg0iK2gw3J96ZJ8Xop+YQxxOPXpVquPSekI9anBkCKiHKaCggpddgyOQFBDsEGBFv3VPZz9FEagxL6TSFtbboq0bcxEFLbtxxdq54ce7fBOGfsSZZFbXP8T2kMcvQBfrIJjb1FYboq7Vr9p/RZ40b+KaUOW0b6t8dC92UzOeMhtK0p53NCOmLtjWkAaHCnwCWHkBsQUtouWSZHH6UxKOHgnJB2W0eOrlVrjr3bYJwz9iTLorY5Abg0Bjn6AD/ZhMbeojBdlXat/lP6rHEj35tShy0j/dtjofuymZzxENrWlPM5IR2x9sY0ADS4U+CSQ8gNCCltlyyTo4/SGEQ7uG9/u9qzcWO156CDqj0331xVv/zlKC7ZSz++Qiok9m5tMM4Ze+trnf+vnABcGoNc/6Pxr7E3fzRXq0Wr/5Sea9zI96bUYctI//ZY6L5sJmc8hLY15XxOSEesvTENAA3uFLjkEHIDQkrbJcvk6KM0BlEODjJ6/fVV9cwzVfXf/zvvKan2XH65E9Ie48jRtarNsXcbjHPGnmRZ1DYnAJfGIEcf4Ceb0NhbFKar0q7Vf0qfNW7ke1PqsGWkf3ssdF82kzMeQtuacj4npCPW3pgGgAZ3ClxyCLkBIaXtkmVy9FEagxgHt4eHMXbsqPZs2VL/VS+8UO0544xqx333FX3KPke/vkK63lJtMM4Ze+trnf+vnABcGoMc+wQ5jX+NvfmjuVotWv2n9FzjRr43pQ5bRvq3x0L3ZTM54yG0rSnnc0I6Yu2NaQBocKfAJYeQGxBS2i5ZJkcfpTEIdnC/+EVVE9LHH6/2XHZZ/Vexz7e677zTCWmHgeToWlXm2LsNxjljT7IsapsTgEtjkKMP8JNNaOwtCtNVadfqP6XPGjfyvSl12DLSvz0Wui+byRkPoW1NOZ8T0hFrTwOA10zEvvKC1z5RptQA0ODm9U2xr6DidS8Eg9yAsGhVSR9gGvsKG8qgj1IYyMEJ1z5suDwPCa34wAJ/r7xS7Xn3u6v/+vTTRQmp7K1PFnuOV7LINkqvkPIqKeoOTbyWiFcB8XoZknQdWr4tn9U1Xzdj7IQm5OGdiySNvdCyY8on/6MX4tOv0AQhmeVrn6g/JvERCZLGXkxZzxuPgCWkjMvY13RhO9RRmpCOIR7HozmNEk5IR6wnBcWUlwIT7EkE5WuvvTa7l4ceemj9YnzqTXlJPwFp6i/G58Xt6IKEU8Lhxbwcn3L/4T/8h+r9739//cWaVKUQ1PkiEXgGpZdfri/RQ0y5l3QP73Z8/vm6D9QTQxKa7aFXvgYWQ/4oA27gB46kv/3bv61+5Vd+Jfr9rk15IH6f+MQnmod7fzd1iY0feOCBa7ruLdxz0uqaOq+55pp1X53pKbp2SrrmoxRTTPbF+OAMuQ75KpL6Kj8m/6PjKdvvfe97FV84I+njFjGfNJYs/mL8FPTjy0Am9WL8lA8ZSF/4g29+85vxAjRKlIjHpT5U0xBtaX46IR2xKpufKmNlkiAe4kQJZOQ7/vjj6yAAYdAAjekys1KCPO0STLTKw2pYzJdOICBT/3ToY489VuOgT7cKY7AZWjUGR1ZW+FLMLbfcUtczVKZNT/pu8q233lrXF/zlkl/+cu8q6f33V6/u3LlGjnCQsSRBcskeb7zxxuBJisrIhsEQPMHwi1/8Yi0Lq2qQ1pgke/zsZz9b3XDDDbVtcqwvqYzGBm3SNnhApJBJuu6rp3muT9f6FCbkdGg8StdT/twuK9/206FW3yEfCxBeTf/TxHzoN/6HidMJJ5yw9rWftolRXz0QJMabfzq0D6Vy57CV5qdDm5PHvtYYX4xtxjNxUD6nr0zbOfwE9nfaaafVW9lt05e1ldUxxYpSn/JWvcu2dUI6co2yIsfldxEP60RFDptd4DgDyK7exQxk6tNgxvkSFHSMQAqx0uWToXpTViKa/RnbbxEFrfQoUIGLVlAlM44IpwiOliDZMsLypZdeql577bW6qN3ngHBsEiTrFIdInCVc1nbaSMLu3bsr/kh2n98iXLLJOlNV1f3TJIU6bWpb5W/iSP42GW37dp/8bThy3MrYJH78RnZrx+BB4GqS4aaM6AfdkOw+v+2YGdK1ba+uzPxTAGzq2mSZ3K78hMaM/Bq+rTlm6JywZDLc9D/22BAQGjeWjGjMSNdtbdl6ZZP4VMp6mi8CmpRo4ihyh68ROWxKhJ2hL+yOhA6Jh/ZYs0zzt/UtslHZrXyfrdf6VFsXx5vx2J73/dcRcEL6Ohaj3mtzopBDOXiE18DtWn3RQGZwEPS2bt1af1v+iiuuqDZv3rzW/+ZgXjuxb4eyIh44c9VLu0oMZoJNV8BRvqlu6bNW9uQUwQWnpwSOkBw5RR23W2FJOfTAH4ntc889V2MLcerDUU6RtvqcYhvhsrJYZ4vsXKKCdN111131H3npc5Nc2zrYp7+0ZW2T/tFXkkhCH+HCrrAnyMe2bdtaZVGA6SMJnGv2G/lUZmjMIK/V9d/93d/VsqAb/qQv7hcdCnbStQKriA5jhdQWAOsTS/LP4qgxwxZ7Qt9KQ/5HOuPewH/5l39ZGzcaM9QjLLvGjbC3Y0b1aoJIPXbiQBlPi0OAccsYk1+Rv9JYRrIh36LJBzaHnrEZ/T344IN152QbtGXrtj3nOOftpCY2Htv6fH8vAk5IJ2QJGig4UTtQGGQ459CVA5w1AZSByCAksHI5nS2DvY8oWLiaDoJzyMhqBINVQceWWbZ9OUUb+IacYhsG1IM+pAf20QfJBsi2sjpmSRzBlaQg2zVJUVm7RRZIKLKIjLIlhcrSRj7asLLttu33ycK5EJJgx40IextWbe3bY4yb//bf/luNi/TDlsQ5+hySNG4g1MhGOY0ZO65D6ppiHmsH4KYEYcdvhPofdMkE4bzzzqvHCjYqfbCCFYKltQNr2+zjT2PGjfrh29khYP2KJri0hh3hg60f7pMC/WIfTLrxs9Sle0QZiyKafXVYv2JtLTYe97WxaueckE5Q4xi8Ljly3x1OHIIZm3DeOHO2Wg2LrcM6CO67gywr0MbWNeX8kFDulTv11FODnWKzv+jhiSeeWEd4mnlCfouEfnrDhuBJSrNeEVFIKavnIqTNfEO/RT7ABXxSJimlZBH54D6u4447rnM1ua9PBC/0BCb8sZ+SREK5pxF5VnXM4LvsPcjYS0xCH/gu9KAJVEx55WXMsGpm70HWpE55fDseBLATrhzZe/JTfItsR3EwpYel4nFK28tWxgnphDXKk4NHHnlk8MpMs6s4ca2QEhR0yaKZL+Q3Dy+85S1vWXfpLaTcsuV56qmnkruEPgiwEDAcJfvJ6f77q01HHJFEumhTJFABP5WQSv4cXErL8swzzwStrEp2uwUP9MStDApm9nzs/o4dO6pdu3bFFlua/KwyQci5jSEloQ+tkNpVrpS6KMOqaOxbGlLb8nL5CNg3WaTUJj+LHTGh0f3hKXURjzdu3Jgcj1PaXLYyTkgnrFEcMLPE1ERg1cyQgWkvgcTWySUTVkc9pSPAPb16mAndJDvHX/6yfs/oKzt31joh6McmVmr5I7ESqP3YekrkH5Ms6AQ9kZjAab9EP1e1jpz3RGrCJF+GP8tJXKrlz9M0ELDv+k2RWJNK7Id9PciZUlduPE5pc9nKOCGdsEZzBwDBFYfOX85ABEInpOMxpD233VZ/rx6JuBTMPVGeHIGxIpBDSFmplg9jm5uckOYiON/yuYTU2g62lJNy43FO28tS1gnphDVZagBwgzf3tOUkJ6Q56K0vy8Mayfev7ftOfbVvVZTVUe7TQz8pCRuzN+yn1FGqDPeN8UDQGBLjxVfSymgih5BaCbDV3OSENBfB+ZbPJaSStoTtlIrHkmkVt05IJ6z1UgOgREBwQlrOkHL0sfaZUCMOhJKH4FLSmAJ0qeCTgkOzjNt7E5H03zn2rlZL6WNM9q6++bYbgVI+gdvNUiftkq5UPFZ9q7h1QjphrZcaAGMKCBNWRzHRg/XBJaZ9L2mv2P+Xf+HFia1y2NW8mEubYwrQpYJPK0CRB0sRoMhmlzJ7sL339L6UPsZk7z3d9VP7ECjlE5yQjsOknJCOQw9JUjghTYJt9IWCA/Rzz1V79Nohu9/SQ27YV7L7Ota1HVOALhV8uvoac7wUAYppc1nzBtt7DwCl9DEme+/prp/ah0Apn+CEdBwm9XqUGoc8LkUAAjyMxGua/vVf/7V+r2Pvk7586o6nRnvur8oJCJKFG8L/9m//1p86DtDfUJZgfUBCeaqYhzkefPB1ctrSACRUN/A7IW0BKPJQKQIU2exSZcdv8QYF7g3+xje+0f1WCe5/5gto3D/cca97rj4kC/V87Wtf65ZlqTQw3c5gN+iMe7nvu+++7reAcC89dkMM7LmPPoeQKgYGxePpQj4XyZ2QzgXmso1ALCAVvJ+RfV5Z0Za4n7C+p/DrX6/2fPSj1Z6Od/0FE6CWRkJlaSnqhzoQCNYHRPSAA2oiCjFdWy1tqRd7wU70epOWLK2HxrRiVGo1pLWjkQdzCVBkc0uZXbbIZJZ9fMl+6aGHqj3ve1+15ytfqf3XnjPOaCUWufoIkmU/4fzAohAg9mmSrfcU7yfLyy9X2Esd94iB//NTn1XHB2RyCKnHwP2QTz7ghDQZuryCOU+1i4Tyzj1mijjT/dK3v107cY5DRuvt9de3Dsirr7466UtP1BkkS9162D9wSXlvZljt08h17rnnVn/8x388LKy9TG/3W0raVVG735J13aFrr722+u3f/u11xxb1gxdPn3322Ytqfl27O3furA4++OB1x1bxR44fw2/xjltWuloJ6S9+Ub9Pt14V1VWe55+vSUYTawgpX99KTYOyRFacg0tkU5PNnoMRJBTbIQZ2EdI67nFlkD/sZ9/7matXXtkPM2wHG0pJpWPgq6++miLGUpRxQjpnNUK2WHU69NBDq4suuqi+XBUrggYA95DydYk2Qrrnkkuq6u67966Mbtiwl5Tef3+1B1JqEq/RIbBSD/XFphBZQuvkafBjjz22fpn7WF41FCp7iXw4RJ6G5zOb/PH1Gj5L15l4oGnfS9rrh5u031LA2ojdb8laH6Jd2scuzjzzzFquVIfd1UbocQIX71Lliz4f/vCH649B2O+Oh9ZTKt+dd95Z2+hHPvKR+pVaKZ8sLCXLourhMjv+Cz+GP0uZRGKH+A9IBXbG/rr0+OP1FR7eq7vn3e/eS0TxYRs3VpZUYKuf+cxn6i/F3XbbbUmvsBuUZZ1g3T+wVWQAl2uuuaZ//HZXs9RnSmAkEspkBtvh936J++axF1ZJsR/s6Jpr1j34qXjMVwY//vGPzywe7ydbxwHiMV9f/PVf//WkeNxR7WQOOyGdo6p4vySXBuTACWS8IzLWiYoEIjqOtI1g1Jcp9r2zUSuk3IfFpS8S5JNvN4v0EOD56hOEKIZ4hMgyBHGzbREz5Fkk8RiSu9R5ES5swRJxnBPH5v2dcwgX7dp3fiIXxyCGyDuvxJhpYtC03XnJ0jZeIWaXXHJJ9LiZl8yl2xGZQCfgoYCOX0NXMUkkEB+iy6/ryvNOXS6zkrRCyirXQQfVh9ra1mSBbUwalCWgsmbbTX8fUMXSZymFkQgpt3tgO22EdG3iohVSrhaec05VPftsjXNTP23jO0QhJWJg06c1Y2KIHMuQxwnpHLQo47IzZu6HI5iRmoO0SyTyQdIYhNxITeILS9qnzjUS98ore505DzXdd189K2Sm+L/t3FkHz7V8+8ipVkdFPESau2RhMENouZFb7VtZNMBUb1s9WoWjHuUDK5Ey1RFL2NvaGuuxJukUJrINS1ZxmLNMTYestqUbCADkGDKCrc0y8WEAviuuMaO2Lemx2M1SFpFOiKf0Qtv2C1gaN/Mm7LPsd7Pupp/CPjiGbrBbdGX9SrM8vzXZpBx+A19GIqizT134A/kfVrTqL49Bdp98cu+VnoceqsmvndxTjjqRiT98hvUrbbJorJG3TRbKcD+3Ju1tdXCszU8hC/UjF31JIexd7U3xeAmMhCV2RqzR1wXRnfbBem1RhRV2bld78sm9q6IsyFx+eb3IgZ3Kt4DnzONxh9I0Huy4ASv5XPkVjYeOapbmsBPSGapSDq/NMWJwBHaRLTlRrTxYsZpEwZ5r7mvg40T/dfv2vZe8PvrR6t+uvLLaeuutdZsifCrLoGBAMJCHnGiTKKiOtq2I+JqD2JcJxyJiY1fhOA0O5EceBX+cOw6d7bIk4ahgZzFpI3voCEJkSVEpLLoIF7aInpoJGyFQQxiTvyjVrHTfb+omUNi65ZQhe+BkE/bC8bZxY/Ol7Ktuxq8mA3Z8IatNQzq0eae03+d/mmSrCx9hiZ6a/qeJBTiq3kceeKB+wh5iwd8Ld965bqJiy+JLrJ9I8T+2Pu3biY+1vzYyoTL00RLmNrtW3mXelsKouZrZh5n1F689+mhtN9jO/7j11uoPbrqpdaIyj3hs/UXfeIiJx304TPGcE9IZaM0GpibhajYnsqV8lhw89dRTySTEOlG7bx1qU5Y+J/rjH/94P6LQLN/12zqIRx55pCYPQytJMQ6iq90xHt+1a1e1adOmTsKFo+pLIgc33HBDX7bgc9QTSrialYpUc7lzSO5m2bbfPKQAYdEqaBehaCurcXPBBRdUYJybvvOd79Sy6HaJvsDabIvAA2H/0Ic+VG3fvr15ejK/henQJEhky67yWJ9j9/v8TxMY1cvkJNT/YIfN1dEU/9OUxRKIRx99dG0SRN1dib6KWCufxoxdnesqP+XjFi/1va0/Qxihd3ulpK2OtmPUq0WPe++9d20fW+xLU4nHpRcC+jCZ5zknpDNA+1Of+lR15ZVXBgdpBi8rZXYlFeLxxje+cW1lJkVM6j3rrLOq0047Lfjm+i4H8da3vrX68z//8xQx6jLUe+mll9Y3bBPcQ1ObgzjmmGOqn/3sZ6FVjCrftm3bKkgTKYZwNTsBcXv66aebh6N+U5560E0M4Wo2Qn/uvvvu5uGo37R/2GGH1WMGItIcD6GVffazn62+9KUvhWbvzMd9acgRGljbKvrqV79a23zbuSkce/vb3x7lf7Q6aq/6xPqfNlwIvrH+R2NLxC/V/zTlwU43bNhQfeELX9hvtb6ZV7+xI131QS4SxOioo45SlqXbnn766dUf/uEfZmFEvEHvOeQL7HmC/pOf/ORSxePDDz+8yMR7bIbnhHQGGtF7JFlhGJqR2eblRFUm5vU8th67zwydv9gkJ8pKJonLTzFEsq09LkWDDcFB9bblax4TYSe4kFiJIfhNMVkM6E9sP9BDKQxoGyxJ6KVvJaPO1PjHygV2IntvnI76iW2pb9iGxkBoJQR8xk+qvTfb0dhjQqRV0maert8QMrCUrrvyjf24MKD/6Dk0aRJJmVL6SPU/utSLbZTSh/wP4ydmzJBfVyOsvYfiOqV8Y8Io1T/NMh4zNhhXoYn8+DjFzdTxENreovI5IZ0B8hoAqQ4QwkZSQMgRMTcgSJYSA0B4pDpjySJnl4PLosoKg9T2ZRMlMLCENEUe2YTsPaUOlUm1CZUXHrn2rvqEs37HbIVHrq5j2pxFXmEgbGPa0FgtpQ/ZWowMyitZSulDeKT2DXly7V19G+t2TBhpPKZiJfvReEith3KymVTfK1lyxkOO/LMu64R0BghrAOQ6wJIDILebJQaA8Mh1xnJ2uX1aRHlhkNq2bKIEBqlOUbLLJmTvOp6yLWUTcvgpMtgywtkeC90XHrm6Dm1vVvmEQY6tldKHbC2nr6X0ITxy+pZr7zk4zKPsmDDSeMztt8ZDTj2ymVK+N0eWMZZ1QjoDrWgA5DrAkgMgt5slA0KuM5azy+3TIsqXsokSGJRyirL3HDxL2YQcfo4slM0Ze8IjV9e5fcgtLwxybK2UPkr6n1xchEdO33LtPbcPsy4/Jow0HnP7rPGQU49sppTvzZFljGWdkM5AKxoAuQGp5ADI7WbJgJDrjOXscvu0iPKlbKIEBqWcouw9B89SNiGHnyMLZXPGnvDI1XVuH3LLC4McWyulj5L+JxcX4ZHTt1x7z+3DrMuPCSONx9w+azzk1CObKeV7c2QZY1knpDPQigZAbkAqOQByu1kyIOQ6Yzm73D4tonwpmyiBQSmnKHvPwbOUTcjh58hC2ZyxJzxydZ3bh9zywiDH1krpo6T/ycVFeOT0Ldfec/sw6/JjwkjjMbfPGg859chmSvneHFnGWNYJ6Qy0ogGQG5BKDoDcbpYMCLnOWM4ut0+LKF/KJkpgUMopyt5z8CxlE3L4ObJQNmfsCY9cXef2Ibe8MMixtVL6KOl/cnERHjl9y7X33D7MuvyYMNJ4zO2zxkNOPbKZUr43R5YxlnVCOgOtaACkBCSeotMrVkoOgNRu4jhJJQNCqjOWLHJ2qX1aZDlrE+zzSquYJJsogYF1irweR3YXKo9sQvYeWq4tn7UJXqUjXbflbTsmPOTw2/LEHBPOYMTrX2KS8LC6jik/lrzCQNjGyCX9ldKHbC1GBuXFrvGrpfQhPFL6xnjnz9q75Fym7Zgw0nhMwXdW8dj63hi5NK5yxkNMe/PO64R0BohrAGA8Me+p42X4vKdOX6pRQMgRMcVp0p6+KMI7BUklBoACAoM85j2T+mIM73ckydnVPyb2DwyuvvrqWmqwtV8mCumKyNG5554b/Q7TZv04ReohYXPIIn0387b9liz0h37lJMbKscceW1eBXMiC7WIrIUmybNmypbrjjjtCivTm0dijXsakPvHaW2jfSewVuflCzLXXXhtSZJR5hAG6DZ04kY93JYIZRDDV/zQBSfE/6EBf60En8j/NumN/y/9gG9hqaNIYo8yqENIxYKR4HKon5ZtlPGacxPjMWcRj9XNMWyek+7SB88J5HnHEEWuEMEVRDEC+OMNnAzWbGapHhMt+og9iQD1Z6eWXqz894ojq3EMPDV7lIYgwgO23xHGkhxxySHBQ6pKZejZu3BjsxBXcICc4BxLbt73tbdXv/u7vJstTStdd/ew7/swzz9RfaNHL1sGbF+RbvPvKCxO+VvXSSy/1ZR08R3n0Yb+sw77Fu68SBXy+OEO/chJ18UUV+2UdxiNEBLsJSUxyqCP3q1G0xdfN7HikbnCR3obkYSJ6wgknVLfffvtQ1qLn8T/IedFFFwX7nzYB8D9vetOboiYoBFiLEf6PLzUxSchKDz1UffTAA2s7xU5CEn4CWSDHjBnGGV+Ku+yyy0KK9+bBt8tOezPuOykyoTL0AUze/OY3B9t2WztW1/SvRAIrfJH8bUqdEG6+8sXXCkPl6sLoPe95T4oIr5f5/9t7+9DPqvved2gPiT2liSYZH2K0ITqNWDRjalpj5qitRSVpc5y0ZWxKo2kjUUrIEAcq9uQIJtEj/jG0jGjtkaRJOBOCiR1uhjmgICcD9ZpOUTmHMwr1Ri7ciXDlernCzR8Xfvv2tWfev/n81qy9v3vv79N+eC/4fvfTenytz1rrvdd+evHF4u5/+2+L6z784cbtYWnjcVGU9Y5dUndNHPxy4zG2gw01bQ9pWtQzJ9ltRHEaxzK2LUhPzQ4x8DEA8h1sCYSmRkPFYDjxc4cMSOoQq4xG4gJ/6gDUkUokdKp0Ou377y82mGXas6e4/fbbG83yaDZBRkr56ZzUkXbKSxKIOJlh4KsTdYI9Dm5EgV8EgkSCZhfbzLQSj+ol1jX5aVPXSZFab8Z61wx62iHnIm0rinJx5PbBEvsXy1yHnIYTRw346fGu24hP8iLhR7tSe4RRzjEAtp3FzMWT7kvbYq7e0jBiN8u+03DzbmuAgQM8utYPYemP6H/oC5ucoMh2GTipL/o77IJ4ZN+dyvfii8XGDTcUG7fdVlz8gQ+Un4SddYIi/vQT6jCXCaQAACAASURBVF/Ur8m+O+UlCRTbYnJoc7NKTKRjTdv+h7qmXmJdK86qsWYzUw1WcgwbBCt5Y/cqzyIYdS7PW28VG3v3Fhs7dxa333JL8aUvfWl943ECr2l/JbvNjce0TcawLm0s7e+T7K11c9KCVB1pFFw0RhzHmgxyNBgZTtrh6ViuE2XgxZgIi4udgPJQHsj9nThRFIcOnTwS19lz8GCxwecl+VzoqVlfDBcXO4jY0BFj5EXiIorrKhFwMvHu/1UDJoMIIliDWxQBEu1KNeaTRl7nckJYnNVBzHUSUJd4xTHKGjtwvEmQRYGs/LW5bFyRZOXuVNDgUYIscs9xrIy04wFsMxU0aquxjeX4dUyyNpg6cJY4pUse5SQSaEeRl44vc6n8iQ3tgp/6H/KkY1X5UJkQE2oX8lvVNxE/Nhln92W/9Guxj1FcW5b0YfRfuLj+s58VG3fdVYqJ4lS7pg8lj5Sr6gSF+qDPFn/Zr/q1LWkvYKOub6JO4C4xIfuNY42yoPbdpP9RXcsWY13Tz8NprpMAZSq0/1n8Ioc07XhM9aIk2jBSmM3lsWNFwQ8X19nev//kGHiqvTKWUA9qDwsfj0/movX/Isbj2G7jmJHLDHaGTTaxs1z4VeybpCClEafT4MDGYBEImoVjX5XRcKxph5frRAnL/roGW2kAx44VG7t3nzwc1jfuuKOcTSjC5Rs6KQlSAii92HFjyAw6arBNBrDKvLU4ENNjIMPRwCSC69jHZCSScp095Y2zCQqXq+u0s5ffZS/TAYm84WQ3mnFYdj6IXyzjDB/5qeK4zDzlOlvywg+bxk7TAXBZ+cmVX/W0LrtR/5MOMNovUYgdpcJRnNQfNGGpeCVQKL/abZ3gUlrpsuzDTomKzXVmtv71yk7x2GNbvEuQaqfS04kr+8kLeaoS0Aq76GUuPewStrDPjTW5PNTZUdpHKLzqJNa1TnLJ17wOnsRdNSbEK1lqD7k0F8VoM+4DB4qCHy6slzPqPGsQHhaVIFVY9avxRAqO7I/tgX3Ldkpv3vG4yj7IP+VapE0sk8mkBGlsXDpzzcFVI1dHnxpNbFwMmk1d2olGwdU0jtIfInTHjrIhbuzbd1qcZiJJBam8xDKwTplpFBps5G8Vy7SDEKe2M4KanaHM1HVdB69y5eo6J2Dlf5lL5feRRx4pBVfuTH6Z6ce4GVAZhGBJfsgL+VuHi53tk08+WeZFdbzq/ETB/oMf/KBsM+onVpUX+hxOmuOJc5q2+qwoNNWudOJGe+G4xEwaR9V2FCi03aaCK40PEUr/haAo+zPNeKUeax6qjILojTfe2JxZX4WYSLOpvoQ+lLyIU91Yk8ZBvcX+J3dSlgtDmrGuaTNsL8o2qed4UiNbiicEab5y24tgVMaLzTApE5a59NiXClL5S8vQeTxWhHMsFzUeawxhyRhIP0nfvaoT9zkQlEEnJUh5EKSN4IqVCy2M5td//deLd7/73ZuXhbpUAB3U9u3bizvvvLM8e2kdxwIEqdKkg7jwwguL3/7t3z7jUp38rGpJB/Frv/ZrxRVXXLE5S9o2bTVCbvpu0xmndY3w4IGMz33uc22zMJd/BiTOZr/4xS+WHcpckc0ZGJbkg/yQr3W7Bx54oNi1a1e3NrPgzH//+98vPvKRj6z03mOK8KMf/ajsO5oKrpygQYj+0i/9UvHJT36yM0sECv0X/VgbwRWrYRGClPgk4s4666zNW6BiOqteR4iee+65rcaaNI/0P5dffnk51jQVE7m6pl+74IILSoGcptFlG/uDM3HSX3d1czMKQlTCtCovVYJU/ucejxXRApaLGI9pD3/2Z39W/OIv/mL5/Aj9+FDcpASpXmOiyylNKkmdHWebNHiMFwNfqwuX6bl/pmyQFRniDInf1Nxo6npqFefy1hJQ/8Mgg7Bs6uIsM2G4DYR963Rlv5Vesq/IUHrJPvVG34yfMbl56xrRh5vFrgkz7I34iOsP/uAP1j+mhMv08ZJ9riyzBGkuzND30R54+wntnAkFtofgJilIu3TGVCiNUp3EWis3PsgU10OmTpw4UfBj0HnqqafK9XB49KsSpIOv69HXlAvYhoD6n64CjJk3XJd20SafjfzGB5niegh87JRgRQz94z/+YziydbUrj62x9Gtr3rrmih5uXkEaL7MzBvZikgO70C0ecT1UIa+1e/vtt8sTN8rA+lRcbA+6/arN1eF1cbIgbUlenUTLYCv3fuDAgYIfLq6vPCNrSnAeQaosD6WulV8vx09ANhkHnC6l7oUgbZBxtWO8xvU06Lw80vj6sL2ouu4qSON9jfCV64UgVWZqlrt37y50QhPXa4KM5lDaHjTDzZXeNldWVg3EgrQlcXUSLYOt3DsidN++fWWDZClxuvKMrClBDV7zDLxDqes1IXayayAgm0wHnLZZmaddtE1rHv+0Y0QFP7XpXHzz8sjFue59i6rrtoKU29SYTYtPfkcWQxKk3/nOd0rb4d5zidNYlrGuV7WH9AHivpXfgrRljaiTaBls5d4RoDt27Cg4M2RpQdq+CoZS1+1L5hBDJSCbrBpwmpZrSIKUPoyfBWnT2t3qr40gRbAwi8YtEsyq5dyQBClCVLZjQXq6NvWGAd4s0CdnQdqyNjQgtAy2cu8IUInQuL7yjKwpQQ1e8wy8Q6nrNSF2smsgIJuckiAVZrVpbcflvDxiXH1ZX1RdtxGklJ0Z0jo3JEEqEYoo1Xpd2cZyrGl7qDrpWBcHC9KW5NVJtAy2cu+HDh0q+OHi+sozsqYENXhZkK6pApzsUgio/2k64FRlYp52URXnMvYjJOTiuvbxoAoPryCi/uIv/qJc17GhLxdV120F6SxuQxGk3/jGNzbtIa7PKt8Yjs/bP6yLgQVpS/LqJFoGs/cVE7AgXTFwJ7cSAup/5h1whiJIZ0Fl1ou2zpJfTrTOiqOvxxdV11MVpH2t11Xka97+YRV5zKUxSUHKDdt6JUYOSrqPV0Zwgzf316iTSP14u18EJEhd1/2qF+dmPgLqf5gRbPM+ZL2uh6804cYkSHWv/FgFadu6xj/9nuragnS+NjfE0BakA6g1vjDR5usSVCovlY2f6PvzP//z4uabbx5AaaedRdf1tOt/rKX/m7/5m+LKK6+ceZ9fLD+veUGUcKkVYcqJNdvPPPNM9LaWdcTTZz7zmeLrX/96p/QlQnmTCL95Zkhhc/fdd5e/PtxbR11fddVVres6PpREXb/nPe/p/EWuXKXwwBM/u/4S0MNp/c1hPmeTmiGlA77mmmvKM0cqrMrpDJOGrc+2IWSZJeV7vq+//npVUO/vCQHXdU8qwtlYOIEHH3ywFJR8FrLO6UlafbsekYWQoF979NFH64Ku5Ji+HY5Qpl+lf20zYUAmJUi5l5SrIl0FqV4eLmEb+/6VwKhIBDbkZdbT0Lm6JiwnHt/97ncrYu+2Gzvqg2DvlvvphELHDM1NSpCqctIZA+1nySUxOgC99gLhSoeOkNVXTqJ/r/ebgOu63/Xj3HUjwGCzd+/eUsSlnwDlmPosCTwJLi7lrnug0mdMEaH0r8oP/WuTCQOIIYgQaf/0T/9U8MAKjndOap1bsmYJdsKQJrcv6POKElu6Osaxdff7MJJgb1PXmhEv4fjPBAZAYJKClHqh49EZpGZB2UeHTQcQj/f5ywYDsLG1ZzHWpet67dXhDCyQQCqoiBrRoj4LYRYF1wKTbh0V/SrCLxV5TALE2dG6k0gSjeK6KhO0eQQ7kwupiCMMIjgn8vSZTJa4KJ4lnKvSXPb+WNewVP5U1/E4gtrOBIZGYLKCVBWV6yTp8OI9V/Lr5bAJuK6HXX/OfTWBKNIQY4inOkFWHdPij+ROCNNUEFNxdjQXpovgyglyZk7p36sugyPmeG4gPjuAX8I0mXVNy7bo7XR8qhLXi07X8ZnAsglMXpAKMGfCPCxw6aWXlmfxOgPVcS/HQ8B1PZ66dElOE0DEcavR+eefX1x44YW9EU/kp+nlY82OxlummFU977zzyv45N9t5mkD1mkQcD/gg1JvMdmq2VLc5SOS///3vL15++eXqxFZwRIJddV0lrleQFSdhAgsjYEGaoHz22WeTPd4cKwHX9Vhrdtrl4kXxb7zxRi8g/NVf/VVxzz33lHlpehkZsYUIjJfbEV5Nw1cV/Iknnih+7/d+r1Ve8Iw4Ji+6NM5MbldhXJW3rvv7VNddy+BwJiACFqQi4aUJmIAJmMBCCTAzyg8Bx72jbRwClPtLcVwun1eQ6h2uxKf3FDfND1fMNAtJOfoiSJvm3/5MYAgELEiHUEvOowmYgAkMkMA8gjQWd92CNObFgjTS8LoJLI6ABeniWDomEzABEzCBQMCCNMDwqgmYQC0BC9JaPD5oAiZgAibQlYAFaVdyDmcC0yNgQTq9OneJTcAETGAlBCxIV4LZiZjAKAhYkI6iGl0IEzABE+gfAQvS/tWJc2QCfSVgQdrXmnG+TMAETGDgBCxIB16Bzr4JrJCABekKYTspEzABE5gSAQlSvrLEC+7bON77yftIcYt+yp742jheks+nRnF+yr4NOfs1geYELEibs7JPEzABEzCBFgS+/OUvF3v27GkRoihynxF917veNfd7SB999NFi165drfLCu0/Tz4hefPHFxV//9V+3iif1/Prrr5cCl48A2JmACZwkYEFqSzABEzABE1gKAYTXTTfdVM4qIjTrHC+fZxZy586dxfPPP1961Sc/EYV33HFHXfCZx/j052233VbGP+vF9vjV16KYHcURhrzdfPPNxRVXXNH4E6QxY/rkJzO0t99+eznzSxntTMAEisKC1FZgAiZgAiawVAISc1Xfkd+/f3/5eU59DQnxyqVxLvMjVHHxS0vzZFZxI04Vd4yPWwX4VCifDEVA4ge/5CeKavKMsGTZxElccxuDZkaJmzKmcTeJz35MYGwELEjHVqMujwmYgAn0lEBOxLFPQhWBplnS3CzmokQpeBCeCMooEBGNEqpxNlPfsU+xMpNK3hGwmklN/UgAR3FN3IhQhZFgp+w5kZzG6W0TGCMBC9Ix1qrLZAImYAI9JVAl4hCmCDvNklZlf5GitEp05sRqVX7Yf/z48fJeU0Qn953iZolrheF2BNZxlB0GTWddy0D+M4GRELAgHUlFuhgmYAImMCQCEmTXXnttsWPHjs1Z0iZlaCpKSQNxh1B8z3ves+WSe0wH8cjM6FVXXVX+NEsa/TRZZ4YVQfnxj3+8kbgmTmZJCaNZYgl2mHzve99rkqz9mMAoCFiQjqIaXQgTMAETGCYBnn7/yU9+0jrzOVGKsNT+888/f1PoIRTfeOONmfdq/vCHPyz4zeOYdd22bVuBsGS9qdMMMfnHPfjgg8WnP/3ppsHtzwQGT8CCdPBV6AKYgAmYwDQJIN5+93d/d/M+TkQoT+OzP96LyX2cCER+q3iACEGKY2ZWbwxoUkO6zB+FdZNw9mMCYyBgQTqGWnQZTMAETGCiBM4777ziS1/60uZ9mDkMerBoVaJUghTxm3s4K5fHdJ9metP93jaBsRKwIB1rzbpcJmACJjByAgjMs88+uywl92LWXSJfpSi1IB254bl4SyFgQboUrI7UBEzABExg2QS4N5TL4ghRLtcjUOvcqkSpBWldLfiYCeQJWJDmuXivCZiACZhAzwnw3k5elcRlcS6PN3GrEKUWpE1qwn5MYCsBC9KtPLxlAiZgAiYwEAK82J73fvJye35NXSpKL7300k5P+lelZ0FaRcb7TaCagAVpNRsfMQETMAET6CkBhCiCFHfNNde0epqdMIhSvYCeB6PiU/nzFtmCdF6CDj9FAhakU6x1l9kETMAEBk5AT6HHB5u6FAlhunPnzi5BK8PMI0gpF2Jb5atMxAdMYGQELEhHVqEujgmYgAlMgQBfU+ITn3qwqWuZmSXlK0mLdBKk+oxok7jj9+x5SIsPBnz2s59tEtR+TGAUBCxIR1GNLoQJmIAJTIsAr3tidlQvwu9aep7SR9Qu0l1//fWNbyNAtJKH+MJ+Zkc/9KEPFQ8//PAis+W4TKDXBCxIe109zpwJmIAJmEBK4Mc//nHBg0g4Zjhnve4pDa9tZiIRtnXvL5Xftku+0MS9rQjm3P2p5Pnee+8tP28qQTwrTNs82L8JDImABemQast5NQETMAETKAXojTfeWPAy/Hlcm9dFdU2H2c7LLruseOihhzaFLwIYsap9CFZuQejycFbXfDmcCfSNgAVp32rE+TEBEzABE5hJAFHHpe55RGnb10XNzFSFh9xsKF4pA6KUtwVwP6ydCUyZgAXplGvfZTcBEzCBARNoI0r15DozkXrd0zzfmu+CLd4v+sQTT5Qzp1y2pxx2JjB1AhakU7cAl98ETMAEBkygSpQyK8m9mXzNiUvmzEJyPyczkRzjx/2j63DcKvBbv/Vb5eud1pG+0zSBPhKwIO1jrThPJmACJmACjQmkopR3iyI2uaTPp0WPHz9exoU/LvHzmqcPf/jDxU033dQ4DXs0ARNYLgEL0uXydewmYAImYAIrIJCKUiXJk+vcp8nl+bPOOqu45ZZbykv2iFY7EzCB/hCwIO1PXTgnJmACJmACcxCQKP3KV75Szo4yS8qT69ynyWVyOxMwgf4SsCDtb904ZyZgAiZgAi0JcG8oDy5x/yjrdiZgAsMgYEE6jHpyLk3ABEzABEzABExgtAQsSEdbtS6YCZiACZiACZiACQyDgAXpMOrJuTQBEzABEzABEzCB0RKwIB1t1bpgJmACJmACJmACJjAMAhakw6gn59IETMAETMAETMAERkvAgnS0VeuCmYAJmIAJmIAJmMAwCFiQDqOenEsTMAETMAETMAETGC0BC9LRVq0LZgImYAImYAImYALDIGBBOox6ci5NwARMwARMwARMYLQELEhHW7UumAmYgAmYgAmYgAkMg4AF6TDqybk0ARMwARMwARMwgdESsCAdbdW6YCYwfgKPPfZY8YEPfKB46KGHip///OfjL7BLOBoCL774YnHZZZcVN910U/HTn/50NOVyQUygKwEL0q7kHM4ElkDg0KFDS4h1fFE+//zzxc6dO4u77rqrePXVV4t77723HNyffvrp8RV2jSWyPS4e/ltvvVXaLfb73HPPFdgswhQb5pidCUyVgAXpVGt+AuU+duxYceDAgaJcvna4OHDqd+L//b8219l37K1/aUyDsI3dsWNFceDAyR9CM24fOFAw2JO/EydObEbJtl01gZ/97GfFbbfdVlxzzTUFM0w4BnUcs0y33nprccMNN2weKw8M7G9pdoudyR5ZJtuHvvUt2+OSbWX//v3FBz/4wYKZfRw2jAhldp9ZfoSpji05K47eBHpHwIK0d1XiDC2KAOJux44dpSDd99+/WWz7h39fsJQgZXv3Cw82FqSv/j//RylkG+fv2LFiY8eO8lecEqQbu3cXxbZtpTBAkCp/EiG7d+8+QxQ0Tm/EHhmw77///nIwP3jwYFlSzZLu3bt3S8kRqMw+sX+IM05Ls9sTJ4pofwjSjX37SntkiSCVPXKSRD5kj9inXXcCR44cKcWmbDLOksbL9ZxwMevPCRf2bWcCUyJgQTql2p5YWTWgUmxmQRGgcTaUbWZIcW//fz8vvvO/P1f+WMexzTphWO46+petBCxxIABKEVDGWJycoUKQnnIM+HGwJ892WwlwSZNZJQQpwjQ3S7o1xMktzUaxHJJbqt1iX8H+yll7tk8JTtvjYi0FsXnLLbeUv+PHj5eRyy7rZkIRo4hSrgZg73YmMAUCp0fGKZTWZZwUgdzAzgypLt1HQcpMafwhQhGgiFLW+bWdUQV2KUh37Ni8VLo5Q3WqJlIBMKkKalDYG2+8seDHoBwva2qWdFYUzETdfffdxeWXXz7La2+OL9VuJUhZHjiwOUNaJUh7A2WAGfnRj35UbN++vWB2FNdl5h47J45XXnllgAScZRNoR8CCtB0v+x4QgTYDu2ZPJTy5rI8gZVsuCthyX3IP3ub9eeGeUAtS0eu25H5QBnI9kdzmwQ9mpwjLkhnWobil2q0F6crM4Jvf/GZxxx13lCdSzHS2vbeZ8Di1gZVl3AmZwJoIWJCuCbyTXT6B3MBeJTBTQUruuEyvGVW2OwtS7huVkyA4te0ZUoHJLzUYM9MZ77XL+966V4JgDIJ0YXab2N+sS/ZbiXqrDQHZH2H0AF6b8NtO3VqhNtAmrP2awBAJWJAOsdac50YEoiCd9VBTvFyvB50O/ex/LQXpn7/4N2V6CFKONX7SfsZDTURqQVpflfMMxhIEQxaki7TbN/63/1n7UBMPOdke6+2xzVHZX5sw0a8FaaTh9SkQsCCdQi1PtIxRkOq+UZZ6yl77mH1iNjQ+1MQ+PVXPMRz78NPYxdc8ZV77RDwWAPU0py5IZaMLsdv0FpPMtu2x3h7bHLUgbUPLfk2gKCxIbQWjJYAg1Wts+ljI+NqnPuavD3maqiBdh93aHhdr8Raki+Xp2MZPwIJ0/HU82RLq3Z7xtUp9gpF7MX6f8teHvExRkK7Lbm2Pi7V4C9LF8nRs4ydgQTr+OnYJTWCwBKYoSAdbWc74FgIWpFtweMMEZhKwIJ2JyB5MwATWRcCCdF3kne68BCxI5yXo8FMjYEE6tRp3eU1gQAQkSHmfKN/51kvGmxSBr93wNZyhPWXfpGz2038CEqR80IFP2epLY01zzjtMcWoDTcPZnwkMlYAF6VBrzvk2gR4TeOCBB4pdu3bN9dlDvs703ve+t7jzzjvLkvLpRX2Gsc07SREGF1xwQY9pOWt9IsA7Q6+88sqCT9bO4/74j/+4OP/88ze/MoYg5QMNbeLFzi+88MLihRdemCcrDmsCgyBgQTqIanImTWAYBOLnEZ988skt36BvWgJmlDR4P/7448XevXvLGSbixjFLymwpX23Cb5VDWDC7dOuttxavv/56lTfvN4GSACdAd911V2lrP/zhD0u74QRI36Bvikn2id1iv9jqQw89VNoqaWCP2GVdvHwIAvsmLA+b2ZnAFAhYkE6hll1GE1gyAWZyNNDqqzSIRYlLBtYmM0P4wW96eTOKS9IiXgb53IwTg3kqYpdcfEc/cAL79+8v7Y5bPHDYEC6KS+0rD2T+1AZSERvFpdqAbkHBTtOTKr5fH0VsJinvMoFRErAgHWW1ulAmsBoCDKaaydFgS8rMBCEWGehxGqyZGZJgjTlMBWc8FtclWDU7SjqIVznSi+lqv5cmkCNQJTi5f5MTLOwWV2dXOcGZSyu2Ac2OEq/Wuef5mmuuKfjuPXZtZwJTI2BBOrUad3lNYEEEmMlB/OlyZBotAzUzQMz2MPDjdEmfS6MMuvx0mVSX5NN40u04O0oecFXCIg3rbROAACJQ9yNLEKZk4skPtix75gEl2Sozqm1nM+PsKHHSBhChiFFEqZ0JTJWABelUa97lNoGOBBCEF198ceOZnNzgz0B+3nnnlT9dJm2bHQ3kH/jAB0pxUSUs2sZr/+MmwMNGl1566eZJUl1pdfKD6OThOByz+dddd13xrne9qzyZwg67OGZHzz333AL71YlVl3gcxgTGQsCCdCw16XKYwIoIcOnxoosuKlPLXX6vyoZmMbncjrvnnnvKX5X/pvtfffXVpl7tzwSKa6+9tpzhZHZSl+RnYUF0chmfWUzC8Hv/+98/K9jM4zxsh+i1MwET8LfsbQMmYAItCTAYc6kex7LpoK5kmGliEObez3j/p457aQLLJKD3enaxPy6pcxIW28Ay8+q4TWBKBDxDOqXadllNYAEE4mDcRZAqC10EgcJ6aQJdCcwjSJVmbAPa56UJmMB8BCxI5+Pn0CYwOQJxMLYgnVz1D77AFqSDr0IXYKQELEhHWrEulgksi4AF6bLIOt5VELAgXQVlp2EC7QlYkLZn5hAmMGkCFqSTrv7BF96CdPBV6AKMlIAF6Ugr1sUygWURsCBdFlnHuwoCFqSroOw0TKA9AQvS9swcwgQmTcCCdNLVP/jCW5AOvgpdgJESsCAdacW6WCawLAJRkPJexjYvBueVOXySkXdA+in7ZdWQ460jIEHKi+n5NXV6VRkvsY9toGl4+zMBE6gnYEFaz8dHTcAEEgIMxu973/tKUZkcqtxEtKafCP2TP/mT4stf/nJlGB8wgWUQ4NOff/d3f9cqan0ml5MohOlPfvKT8itLrSKxZxMwgVoCFqS1eHzQBEwgR2Dfvn3lN7xnffKQwZtv3fPpRX0iVJ8Svf766wu+VGNnAqskwDfqr7zyykaf/eRF+FwF4FvznFTJnnndWVtRu8oyOi0TGCIBC9Ih1przbAI9IMAAzUDNgM3AnToGfoQonwrlEj0/1tnHZ0TtTGCdBDhBwhZzl+1zth3tGWFqZwImsFgCFqSL5enYTGByBNJZJAAwC4pY5fI+ToM/s6V2JtAXApwk7d2794yTJE6cNPvPfc/cd8q9z7LnvuTf+TCBMRGwIB1TbbosJrBGAgzgzDghOjWD9NxzzxXcs8f9o8w62ZlAHwnoNpJbbrmlPJkijxKr2C92bGcCJrBcAhaky+Xr2E1gUgR0Wf6SSy4pPvaxj5UzS8ww2ZnAEAhwKwknVZ/4xCcK7hPNXc4fQjmcRxMYIgEL0iHWmvNsAj0n8MADDxS/+Zu/2fNcOnsmkCfw7ne/u3j55ZfzB73XBExgKQQsSJeC1ZGawLQJfPOb3yzuuOOOaUNw6QdLgNlR3y862OpzxgdKwIJ0oBXnbJtAnwlYkPa5dpy3WQQsSGcR8nETWDwBC9LFM3WMJjB5AhakkzeBQQOwIB109TnzAyVgQTrQinO2TaDPBCxI+1w7ztssAhakswj5uAksnoAF6eKZOkYTmDwBC9LJm8CgAViQDrr6nPmBErAgHWjFOdsm0GcCvJOUd4/amcAQCfDqJ783d4g15zwPmYAF6ZBrz3k3gZ4ROHDgQLFr164yV4888kjBtp0JDIXAtm3b7bBXbwAAIABJREFUypfg8z5d1u1MwARWR8AtbnWsnZIJjJ4AApSB/NChQ6UYtSAdfZWPqoDYrk6oLEhHVbUuzAAIWJAOoJKcRRMYCgEE6De+8Y1ix44d5dKCdCg153xCABGKzfKzILVNmMBqCViQrpa3UzOBURPQYP6d73xnc3AfdYFduFERQIS+/fbb5SypBemoqtaFGQABC9IBVJKzaAJDISBBSn6ZJWXbzgSGQkAilFtOtD6UvDufJjB0AhakQ69B598EekCAh0B4qv7nP/95Njf33ntvceTIkewx7zSBdRN47LHHKu3zueeeK7DfKtted96dvgmMhYAF6Vhq0uUwgQUQOHr0aPH1r3+9eP755xvHht+dO3cWTz/9dGUYXqFzyy23lAN7pafkAGG+//3vF48++mhyxJsmkCfwl3/5l6Ww5ASpicPfbbfdVnsyRTwPPfRQccMNN7T6vj1Cdu/evUXTvDTJr/2YwJgJWJCOuXZdNhNoQYCB85prrin+8A//sFxyyZJBmNkh3iv605/+9IzYGKgJkzt2hudTA3vOP7NPDODEd+uttxbnn39++fv93//98n4+z67maHpfJIDtfOpTnypPfM4+++yCd4kiNvfv3589wdKJFLbdxNX5P378eMHHILhKgH2r7ezZs6fAhu1MwARmE7Agnc3IPkxg9AQQhMxgIgqjk0hkYOfrNQhF/DHzw8CLWG3rNLB/4QtfKAdwZlfPOuusTfHLTGt8KTl5I60XX3yxbVL2PxECuS+DIRIRm7JViUS2P/e5z7U6kRJGzah+8pOfLO6///7SZrFdxO8dd9xRcOkf+46Off5IRCTidRPIE7AgzXPxXhOYFAFmJXXJnfWqGU+EIrOVzJxee+21nRk9++yzBbNYDNZ1QpNBnuOavUVk2JlAJIA9YrOcuGDDCMUqxwnWgw8+WLzjHe+Y657Q7du3F5///OfLEzjSzbmYF/JUl69ceO8zgakRsCCdWo27vCaQEGD2BmGIi+uJt3KTwRdRiEBktrRqMM6Fjfs0QCu+eCyuI4x1715cj368Pl0CzEZiH9hRXK8iopMfZvybXqpP48IOuVqAU3ypH21zQsXsLS6u67iXJmACpwlYkJ5m4TUTmBwBCUMKHterQMTBGCGQXuKvCpfu5xInwpb7/mZd9mfQJy1EcFxP4/T2tAhgP9zKgV3E9ToKstncJf66cPGYbJarBZyUzXLc4qJ7oOP6rHA+bgJTI2BBOrUad3lN4BSBOCjH9VmAEAHMRnW9Nw7xgCDFKa5ZaSJ8GcybzoTNis/Hh00gzpYjDLEj9s1ystl5Zvhls4prVprYLEKYNhPXZ4XzcROYGgEL0qnVuMtrAkVRztgg8HDM3mi9CZy2M0RpnJqJjbOtqZ/cNpdYudSKa5vnXHzeN0wCiElEISc2rCP2Zl06V0njrGaX2cpos5ptVdx1yzTPyn9dGB8zgakRsCCdWo27vJMn8OqrrxYXX3xx59nGroOywLe5XK8wWvIKH56Sxn3lK18pX1GlY15Og8Dll19eHD58uLRfHmbS5fCmpZeQbHNVQHFrVjQKWx2btaTdkDbLV155pbjwwgtnBfFxE5gUAQvSSVW3C2sCJwnwUAYDI5fCmb1p63hVE7NSGqCbhu9yuT6NW28D6DLDlcbl7eER0Aw7dtvlHmbZLOHbPpgnMas42tKjzdDu4mx/2zjs3wTGSsCCdKw163KZQA0BHiTi0ntXJ1HA4KonjpvE1TVcGjf34vHaKJZ20yIQT2q6lDzObkpgNomna7hc3H7iPkfF+6ZOwIJ06hbg8k+SAA9YcB/bGe7gwWKD+zQRqzUzp1EU6CGPM+LK7Jjncn2MzjNMkcb01mVHXUsuIdpmplN+ozDtkj4nUczMdrky0SU9hzGBoRCwIB1KTTmfJrBgAgyKDK5yG3fddVKM/qf/VGzce2+xsXNnUdQ8ucz9nLg777yzOPfcc8v74xjoq35XX311OatJGC67M7va1c3zHsmuaTpcfwjMO8PPpX4un7/++uubXwmrslvt/5Vf+ZXimWeeKdtM13eYQtAP5PXHjpyTfhGwIO1XfTg3JrAyAltegn/kSLFx6qn7jRtuOJmHsK8qU4hK7if93ve+V97Px0Bf97v99tvLb4tXxddkvy/XN6E0bj+VM/wti81DUY888kitzcqen3zyyfJka96ZTV+ub1lJ9j4ZAhakk6lqF9QEthJgoGX2p3R8bvH++wvE6MbZZ5fL4vDhYuPUF2m2hjy5xewql+vbznTOO7vJ7CpCwm7aBPRgXlcKW07IGkbC7KY+U9owyBneuPd5XlF7RqTeYQIjIGBBOoJKdBFMoCuBzcv2YTa0yQwpAypitun7H2P+mOFs+7oexK9uL/AMU6Q53fV42Z57mts84KaH67rQ63L/strJlpPALok7jAmMmIAF6Ygr10UzgVkEorjbuPXWgvtIi+eeK4rHHis2eOgpc59nF0GZ5oM4mF3VQJ0eZ+DmLQAIV2bCEM48VEI4PxCS0lrvNpfPqS/e64nQQyjqvktmA7dt21Z88YtfXHgmo7hjtvOss84qvwCGTXN/M/nKuS7vH03jie/DTY8hjkmDPGHjlF8z+l1mZdP4vW0CYyVgQTrWmnW5TKABAS5BfuxjH9ucfSyFKJftEabhgacY1byX3BUXs6zcf6pL/sw8sc0AjqBB2KQPPyEEbrrpJkXh5RoJfOpTnyrrCtFFfSEEEaScSCAW+enSNMfZXrR73/veVzz77LOb0UoM8vEEiUHSZj9ukQ8UxRlaZu95L24UxZxARVGMnW/fvv10W9vMtVdMwAQgYEFqOzCBCRN44oknivPOO6+cdWQmkpkcRAXiIXcJlIFeT9cvAhuDNIKBJYN6nDFlPZ1p4is9ejH+ItJ3HN0IUFfYS7QRxKeEqC6Jc/KCGMQ/JxssF+WIi9nyD3/4w5tPyiMSObHRSQ5pyZYRh9hazPO8eYlXGJQOcZI3xC8cSJOZ4l/91V8t/uiP/mjeJB3eBEZLwIJ0tFXrgplAPYH00iWDOGJPg6hmexAViFBe78SAv2iH8LzuuusKnmImfgZw0kbAMOCnM02LTt/xtSeg2UHEHe8EZVYb0UXd8ZMgRRxKAC5ydjK9h5k0EITMzmKviGXlh7z8/d//fTljqhnb9iXOhyBdTuIeffTRsszxFhNmTEmbfC063XxuvNcEhk3AgnTY9efcm0AnAk0fzGB2C7+I0V/4hV8o74tb5CyXMs+A/ju/8zubl3slYnTcy/4QoG4QfF3sYBEz7BKBCNw6pxlbROFHP/rR4uWXX67z3vkY+WHmnnTSW0w6R+qAJjBBAhakE6x0F3naBBjImclpI/qYxWTGktlKZsTm+ezotOkPv/R1D/TMKh02xwxqvLdyVpj0OLbr2zZSKt42geETsCAdfh26BCbQmEAXMUrkXHZESOCYeeKSLcKU+A4dOlT+OBbXS8/+Gx2BeT/byaw7JzezTohOnDhR8MNpHbvjVhM7EzCB8RGwIB1fnbpEJlAS2L17d/Hqq69urrPCgD5LCOTwRUGq4wgLvWLnwIED5W6WWpc/L8dDgJlJZijnden9y7n4sCPuTX377bdLm2K7i+3m4vY+EzCB/hGwIO1fnThHJrAQAgzmiFIc6/O4untOEQo7duwo02JpQToP6X6HZZack5OuDkGpez8/9KEPlU/IEyf3lnIPJreEED+X9GVXLPXrmq7DmYAJ9J/AfKNU/8vnHJrAZAkgQvft21cO8PMK0roZLcQC6Rw7dqxcsm03PgK6j3ieksmOEKa8BukHP/hBaZ/cl4og5cXxCFR+X/3qVzdFKfZlu5qHvMOaQP8JWJD2v46cwwkS4DU1n/3sZ7e8T7EtBkQo997t2rVr7hlSZq4QCzkXZ6/ies6v9w2XAHb0t3/7t2UBeKVRl8vn3DuKsK2zJxGSLXGigy1bkIqMlyYwTgIWpOOsV5dqwAR4gp33cjJjxOt1GPx1mbNJsbjciVjQrCgDudabhM/5IS/8ck4PnHAsruf8et9wCTzzzDPlzCW2pZnONqXBhrFlnIRpXfj4gBwzpGzbmYAJjJeABel469YlGxgBnl7ngREePIpOAzniFLFa9f5HHjjRZxyJi5klHA+FaD3G22a9TpC2icd+h00g2kHb1y/J/6IejBo2SefeBEwgJWBBmhLxtgmsgYDuz9P7FXOXNPmSEmKVzyXyNRrNmjJbxYwTA/6s9zsSXuHaFHMRLzRvk5799peAHmzipAe7i5/prMq17JvjEqZVfnP7aRdb0nnuuWLj/PN5Wq/Y+OAHeS9ZLpj3mYAJDIiABemAKstZHScBxCczmwy4XA7lXk1+dffo8dQ7lz/f8Y53lK9eYsBv4oiTcG2flI7f7G6Sjv2MlwAz9AhRlrnXgeVKrhOaKExz/qr2cWVg88rB8ePFxs6dfDC+KHgn6U9/enK7YRuoSsP7TcAE1kvAgnS9/J36hAmk4hNBijBFoM5yzE7huIy/ZeZoVsBTL7ZnlqupiC3eeqv4+49/vPhf/sN/aBC7vUyBQLzsHi/j58qOrWKnsvcm9p3GE4Xvxh13FMUTT5SzoqUwZXb0298uNm67LQ3mbRMwgQERsCAdUGU5q+MhcPTo0eKqq67aFJ9cRm/yoIcInH322eWqLp9qf9MlIqGJKEW0/p+7dpWXRrk8Wsz4fnjT9O1v+AQ060lJOJGqureZ4xzjJ2HatvTYq2x+gxfzf/e7xb8+ZXfycj0P2333u0W5v23E9m8CJtAbAhakvakKZ2RKBB555JHi05/+dFlkLkdyGV2znk04cB8pA/w8l9JJ753vfGf5BD5P4ed+iOS3/82/OS1IK560b5Jn+xkXAWY8EaJVM+3YJzOb/JhF/chHPlK+AL8rhc0TtiNHio1TT+tv/OsL9XGlGD14sGvUDmcCJtADAhakPagEZ2F6BHj4iMEc1+UhI82MzrpcWkc29+BU1v9DDxUb73xn8S/veEfxf5/6FGnWn3dOjgCfj7300kvLDyJgk/yYyeTkhpMm7cNO//RP/7S44oorWt9iIqhbTr6wycsuKzZuuKFcFg89JG9emoAJDJSABelAK87ZHjYBZo8YsLs6Dc5d3gdJmsxucflUs1hVs1z4JS1mUxsL2K6FcrhBEnj00UeLr33ta5uzoXUz/dzvvDnT2aK02OtNN91UXHzxxaXNlkGPHz/5dD1LOxMwgcETsCAdfBW6AEMlcNZZZ9U+SV9XLs2MxpnWOv/pMT7VyD2Asy67Ei4KUWZ1Z71aKk3L2yYQCSBYsaOmVwZ4owQnT9j8t7/97c11bNfOBExgPAQsSMdTly7JwAh0mSlSERmkeRdpl5lWwpA2SwlTxVu1VF6ZSWXdzgTmIYCY5L5pZvirnE62ZOfyR1jEKSKVdmBnAiYwDgIWpOOoR5digAS6vCBcxdRgzXbbmVY9Hc3Arsv2irdqGYWowlf59X4TaEqA20EQl9FxosR7eGfNxuMPsTrLX4zb6yZgAv0lYEHa37pxzkZOYB5hp1lOEF122WUFD5c0cYRDhCJGm86OKl7lt42QVVgvTaCKAIJUH4LgjRPYc5t3lerkLJ1JrUrP+03ABPpJwIK0n/XiXE2AQLw3s0txEYb8eDjqN37jN8qZJl5YXidOGfhJNwrTpmlHIRpfjN40vP2ZQBWBhx9+uPjlX/7l8mtMdQ9FVYVnP5fvt2/fXt5nWufPx0zABPpJwIK0n/XiXE2AAA91cB8djvsyuXzZ5oEhRCWv1XnggQfKB0SYaeI2AGaYeO0OxxCgzITyLsgXXnhh8/5PzXa2xRyF6PXXX1/whLWdCcxLgKfvL7roojIabLWtUxheLVV3X2rbeO3fBExgdQQsSFfH2imZwBYCzGQyCGtGiIGU++F0yZIZySrHAIy/OgGLH2ZDEZ+IU757/+CDD5ZRcnmzLv6qdNmvwf/GG28svvWtb9V59TETaEQAQcqtJDiWbT+HqzB6HVqjRO3JBEygVwQsSHtVHc7M1Ah85jOfKS+5M5OpS+0s2eZSPMt0cOY+OwSmhGxTZl0u01fFHWdKq/x4vwk0JWBB2pSU/ZnAeAlYkI63bl2ygRBgppKZTGY8mSFlppR9CE7NcFIUtrkkf++993YuWdsHmaoS0mugqo57vwm0IWBB2oaW/ZrAOAlYkI6zXl2qgRLgEjyXHTU7qllTvXaJmcl5HEIX0Vv3ZaZZ8Xt2dBYhH29LwIK0LTH7N4HxEbAgHV+dukQjIKDZUWZN+V199dVnXLrvWky9JqdLeAQt9+tx+d/OBBZFwIJ0USQdjwkMl4AF6XDrzjmfCIHDhw93fgCpChH3pnI7QFu3qEv+bdO1/3ETsCAdd/26dCbQhIAFaRNK9mMCIyPADCf3gbJk1pPbBHhQqurHrQOeHR2ZEfSoOBakPaoMZ8UE1kTAgnRN4J2sCaybAA9PIURxXMbndU65n14txcNUPOFvZwKLJhAFaZc3SPA+X06u/NqnRdeM4zOB1RGwIF0da6dkAr0jcN111xV33nln+ZUnXqxf9bvnnnuKc889d+G3DvQOiDO0FgKvvPJK8d73vrf1q8zSzPKxhkceeSTd7W0TMIEBELAgHUAlOYsmsCwCR48eLW6//fZKIRoFKvey2pnAsgh89atf3fwoRNs09KDenj175ha1bdO2fxMwgcUQsCBdDEfHYgImYAImMCcBLrvzwB33N+uLYHVR4p+vjvEqM91aUuffx0zABPpLwIK0v3XjnJmACZjAJAnwnlzuJUVsIjpTxwN2zN7zCrKDBw+mh71tAiYwQAIWpAOsNGfZBEzABKZAALGJ6ER8IkJxuX1TYOEymsDYCViQjr2GXT4TMAETGDABzYZetX178bsXX1w5azrgIjrrJmACRVFYkNoMTMAETMAEek/gX/7dvysuePe7N2dKe59hZ9AETKAVAQvSVrjs2QRMwARMYOUEjhwpNm65pfCXwlZO3gmawMoIWJCuDLUTMgETMAET6EJgY+fOonjxxXJ2lCfqeejJzgRMYFwELEjHVZ8ujQmYgAmMi8D+/cXG3r2bZTpy5EjBl5nsTMAExkXAgnRc9enSmIAJmMB4CLz1VrFx2WVFkbz66dZbby2efvrp8ZTTJTEBE/BDTbYBEzABEzCBnhA4caIo+OFY/vjHRXHkyBmZe+GFF4qnnnrqlLcTxQmFOcOnd5iACQyFgGdIh1JTzqcJmIAJjJ3AgQNFwQ8X15NyHzhwoOB30tvp9cSbN03ABAZEwIJ0QJXlrJqACZjAqAkcOFBs7NtXFMeOnVxKnCaFRozu27evOHbsWLmUOE28edMETGBABCxIB1RZzqoJmIAJjJoAgnTHjmJj9+5yuTlbmhQaAbpjx45i9+7d5dKCNAHkTRMYIAEL0gFWmrNsAiZgAqMkEC/Tx/WksAhQidC4nnjzpgmYwIAIWJAOqLKcVRMwARMYNYFDh4qCHy6uJ4U+dOhQwe+kt9PriTdvmoAJDIiABemAKstZNQETMAETMAETMIExErAgHWOtukwmYAImYAImYAImMCACFqQDqixn1QRMwARMwARMwATGSMCCdIy16jKZgAmYgAmYgAmYwIAIWJAOqLKcVRMwARMwARMwARMYIwEL0jHWqstkAiZgAiZgAiZgAgMiYEE6oMpyVk3ABEzABEzABExgjAQsSMdYqy6TCZiACZiACZiACQyIgAXpgCrLWTUBEzABEzABEzCBMRKwIB1jrbpMJmACJmACJmACJjAgAhakA6osZ9UETMAETMAETMAExkjAgnSMteoymYAJmIAJmIAJmMCACFiQDqiynFUTMAETMAETMAETGCMBC9Ix1qrLZAImYAImYAImYAIDImBBOqDKclZNwARMwARMwARMYIwELEjHWKsukwmYgAmYgAmYgAkMiIAF6YAqy1k1ARMwARMwARMwgTESsCAdY626TCZgAiZgAiZgAiYwIAIWpAOqLGfVBEzABEzABEzABMZIwIJ0jLXqMpmACZiACZiACZjAgAhYkA6ospxVEzABEzABEzABExgjAQvSMdaqy2QCJmACJmACJmACAyJgQTqgynJWTcAETMAETMAETGCMBCxIx1irLpMJmIAJmIAJmIAJDIiABemAKstZNQETMAETMAETMIExEmglSLdt21b4Zwa2AduAbcA2YBuwDdgGbAPRBuYVya0E6byJObwJmIAJmIAJmIAJmIAJpAQsSFMi3jYBEzABEzABEzABE1gpAQvSleJ2YiZgAiZgAiZgAiZgAikBC9KUiLdNwARMwARMwARMwARWSsCCdKW4nZgJmIAJmIAJmIAJmEBKwII0JeJtEzABEzABEzABEzCBlRKwIF0pbidmAiZgAiZgAiZgAiaQErAgTYl42wRMwARMwARMwARMYKUELEhXituJTYHA1VdfXdx3331TKKrLaAImYAImYAILIWBBuhCMjsQEThOwID3NwmsmsEwCfCXm4MGDy0yiF3E//PDDW76S+Nprr/UiX+vKBOWPXwiCj91JAkePHi3ZDLFdWJDaik1gDgKHDx8u3BnOAdBBTaAlgVSMDHHgbVPkVIxKiE1VlEpwiYOWY7eDpjYzZB4WpE1r2f5MIEPg7rvvtiDNcPEuE1gWAQ24Wo5ZiCA6L7nkkk2U9DcqN+tTdJFHFKdT5RFtADayjyG2CwvSWJteN4EWBGjwNH7PkLaAZq8msAACUYgMceBtiiA3CyrBMVUBljIRjzHbQRN7wR74DZmHBWmTmrafXhOgg+IhonPOOad46aWXyhkF7uOUQzDqzJEll9nlWNcxGnLayRPfnj17ykZO/HpYiXBq+FoySPIjjptvvllJlEv2kyf8Eg9+3nzzzfJYzD/rSo98xc5XeVU5lZctCXnDBCZAYCqCNFeV6m+mLsBgIwGW9ts5bmPehy0wzg29XViQjtlKJ1I2CTg6akQbjRPRhkO0qeNGAKoDQ+jxI8zjjz9e+mXJtvxznHjS49pW448zpPgnjihI8cd+ljhtSzTH/BMX+VTasaMlDgQyDn8xjXKn/0xgIgTU9mJ7nULR1WdxsjplJw7Uv37qX6fGhXJrLBh6u7AgnZr1jrS8NEg6Js06UkzW1VmlSwQd4o79dG5ybEtgIgajICQ+RGSdICUe4lAHwTZhYjzsQ/TiT+JX+Vc+WLIvxoP/2OmmccawXjeBMRMY+sDbtW7om9J+oGtcYwhHHwgP/cZQprZloOxyQ28Xp0uiEnlpAgMkkBN0apyzioMgpaPXpXsJUuKsuyyu+OVf6dBBpEIy9SOxrP25/LMvxqNL/iwlZJWmlyYwJQJqe7S1qbQFzQqqz5hSfdeVVSf32AJ2MSWHLVDuqt/QbMWCdErWO+Ky5gSdBq26TgrBiRBl1jPt8Imz7tKY4k8bPZ1DFJJs54Qt+xU2l3/2xXgQsfiXcEaYss/OBKZGQG2PNjQVQUq791WRvKWrT4xXu/I+x7WX8YA2UPXT+DKUUluQDqWmnM9aAjlBJ4HJvZfcWyrHYIYA5UdDjqKObTVi3dvJIBD9sB+nQVH+FT9xRCFJZ8kvxqG8KV+5/LMvxhMHI+WdPNiZwNQIqO3R1qYgSGn7sf1T35R7agJMs6FpndNP0sdO3Q29XViQTt2CR1J+Xc5Oi8PMJINW+qMj19kl95IiFtXZsR+hqHtMY1g6vShAOUYa+CU88bCP/MgRF/skbPHDehSbyn8UreyL8RAHQhSnvLG0M4GpERj6wNumvtRP0f7jb4oCLLKQKJUtTE2c52xILLAT8cn56+s+C9K+1ozz1ZgAwk4dda6TRjDq6XcEnmYl6cDwT1jiYJvj7JPQo4GzDz/EEcUoGURYckyX5JUPxalCkGaMB/8SnzH/hMPFeLSPtPmRD35D7HDEw0sT6EKANpq2DW2PUZBEAaZyapnOmHbhOcQw6rPFIZ7YD7E8i8yzBekiaTouEzABEzABEzABEzCByRHwDOnkqtwFNgETMAETMAETMIF+EbAg7Vd9ODcmYAImYAImYAImMDkCFqSTq3IX2ARMwARMwARMwAT6RcCCtF/14dyYgAmYgAmYgAmYwOQIWJBOrspdYBMwARMwARMwARPoFwEL0n7Vh3NjAiZgAiZgAiZgApMjYEE6uSp3gU3ABEzABEzABEygXwQsSPtVH86NCZiACZiACZiACUyOgAXp5KrcBTYBEzABEzABEzCBfhGwIO1XfTg3JmACJmACJmACJjA5Ahakk6tyF9gETMAETMAETMAE+kXAgrRf9eHcmIAJmIAJmIAJmMDkCFiQTq7KXWATMAETMAETMAET6BcBC9J+1YdzYwImYAImYAImYAKTI2BBOrkqd4FNwARMwARMwARMoF8ELEj7VR/OjQmYgAmYgAmYgAlMjoAF6eSq3AU2ARMwARMwARMwgX4RsCDtV304NyZgAiZgAiZgAiYwOQIWpJOrchfYBEzABEzABEzABPpFwIK0X/Xh3JiACZiACZiACZjA5AhYkE6uyl1gEzABEzABEzABE+gXAQvSftWHc2MCJmACJmACJmACkyPQSpBu27at8M8MbAO2AduAbcA2YBuwDdgGog3Mq6BbCdJ5E3N4EzABEzABEzABEzABE0gJWJCmRLxtAiZgAiZgAiZgAiawUgIWpCvF7cRMwARMwARMwARMwARSAhakKRFvm4AJmIAJmIAJmIAJrJSABelKcTsxEzABEzABEzABEzCBlIAFaUqkp9sPP/xwT3O22mwdPXq04Lcud/PNN29508Q68zIPA/Idn46kXKlbps01ST/Nz1C2I1fWU7dMrmlaQ9m++uqrt9ijGF5yySWVRXjppZcKhTvnnHOKu+++u3jzzTcr/b/22msF/vrQZg8fPpwtL+U+ePBgZRmalBk/cCMulmwPzd13331Frk/KlYP2JHthiU2kLu23iX9IrimPWfZB+4is4jrtZ92yktwqAAAaXklEQVTuzN5y3TlaQ/pUCp3VLEfjbtKZpQ0kVrrWc+nFRpMeX+YgdsF//Xyx7R9uPeP3hRcfLT763FfO2I/fTz3/tVm4Oh+v4wD/JnXQOfEZAckbPznqSXVatVxm3RX33FMUiJ70d9FFRbF//5n75U8FKPCybUuZdGiZ+aYOSTfWJTaVs0NsEFvMHcN2l+Keeqqa3axjpzIkO07zt0yuaVpD2K5rQ1XCgTAMoOonEXGIzdg207KrPqLNpX5WtU3eq/qLKlFNWaPwxh/iKwoJ/MCMY6xTZsJUxbmq8rZJR31DXV3G+CS+xfPxxx+Ph0sOOqblkER6Ux5N7IN2IgbpkpOkdbtJC1JVTt0ZaVpBVGLsANLjcVsdIGEwFpyMi32xwSkvMpJ4jHBdBrE0jpi3dP2/vfk/Ngd8BEDqJAaWIQD+8+vPFP/x+H8pk5zFAX781uVgmuMa8x3rKnaWsoGl5P0TnzgtoP75n7cmsWfP6WOIqcSltqjDsRzaV7ekXpqGUTvI1WU8QUrTiydI2Oyi3RknWlHwI/Cji4Iff4nDTmCbuqaM0nBj3UZApCKCstbN7tHeUpEFV3jnxAbxazY1Z3OrZottpP0BZdpDW61wlIHyxXJrplVBiCM6tbMck+ivL+uUjXqi7nP9bJpPyjtrPOZ4yiWNp6/bbXg0sQ9YpPYvIdsHBmf2ln3I1QryoIba1lAVrsmgogGJTiR2PoqD/WpM5INt/Qib7tMxGmsT16RBK551ClIESJ0ghZ3Kni4jV5VlmUuY5rjGukptI4rSpeVtQYI05jWybtJOsOu07FXlVRtgmbp1CVLE6LIEKe088tS62n/KYErbObHEvtyl1zouVTZFH0GblXjL2VxdvIs+Rn6iqFT8iNG6WSr1MbEtIkLqRCx+23JUftaxZHaXPFf1s2me6K/40Y5yYwH7aGswoG/KcU/j7NN2Gx5N7CPX1rChqisRq2YxWUGqgbcLcBoLRp5rADE++cv5zR3L7VN8TQd6+WdJfE3dugSpxIcEqfKtATtlzGCyzgEFpjmu6gzId1pXdcea1s9MfwsSpDGdtBzxWG6demkaBr+wytWlbIJZ+dQta4ZUtwssS5DGcjRlFMNMbZ0BkoGyjUPMcXk6dbRXBuI6m0vDrHoboZTLe5oPhBX+KCtlomw5kcU+7KzqeBpvH7apH4lr8s2vzqk+NVawpK+NDgbxOOxyoiyG6ct6Wx7ku6l9xDISpi9MJilIJRBysxM6JiPONQr5yYWPFU1YxZMKq9hQ0kYU49B6l0Esl3fFly7nEaRRQCAi0kuputyvpcSntuOSy/d1jkbKb5GOzhtWuY49TQd/Oa6yCeo7rSudpXMsFzZNo9O2BWk5uxltSXYmnlHM4k/iM93PMe5ZLZ0v2QvfSpcIh7TPnJUB+uO07SFqJWwlYBbdf8zKV5Pj5HHWeEI8MEFAqC+p6rM07sBR5W+Sj3X5Sfvgqn42lz/qE3YqcyquiBsBT5z4YTKqilsu/nXs68qjqX2oTLCCR1/cJAWpDDPtvNjGYNVhaRY17SjUsc2qSKVDnGnnqrQ4luYjZxyz/ChPxFf3q4onCtI4qKfriM/oJEYlJNNtzTwpDNsIBfzzU/ypeJD/dEk5VT/psXm2NSDM6qiqOsqmgrTSZvSwUd0yc5/iZpmjIK2LY4H3kEb7rrO5zTyGFdlrri5lQ7KNqmU88ZGdSUim29gX8chO2cYPLtqh9m1mNQrSOq6ZuhGfzbhOrVS1wdTfVLcRD5opa8qAgRWhFh19boynzuZiuHWsN52lon9iPKJctLl0bIp5p7wSrzDts2NGPPYFVf1sXRko4ywmpIOfJpNAdWkt+1hXHm3sgzJ0uRKxzLJPUpBKaKZGyUCBsdIYcPKXNno6OvzxS4VmrCwNSDl/SotjyxqgVI6Yp6r1KEiZMUqdREEUpBrkOSYnIaA4NPt0xkCfCIGmglTpLGMJLzrwWXWa4zq3IJ23QFGQLuihprZZYkBpast14iAK0jQPsidsToI02m4UnLJZ4tBT+tF+Y9zye4adRkG6oIeaYrpeP5MA/W3aN5/p6/QeBmEEWnoyyb7Yluts7nRsq18jj5UnqiE7lI/+ScKNk2jGD0RFlSMMs6RRmFf5Xdd+ypOWgT4218/OyiO2MyscrJv2U7PSW8bxrjy62AcsYhtZRnnaxDlJQUoj5lfV6VFB8sMyNfB4XJ1DDjrhFE9a6VGQVuUjF2ebfWm+68LGQV1iMvrXgB0HdInP3D7842K87JNg4FicmVqkII1sxb/Nsm5wgGmOa1NBmgsbOXden7AgjSdGEqlxn2wuCl3NpIq37NuCVETWs5SAYtnUIbbSy7T0y7PafNP4l+2P/ioVZLk0JUDjMe1Lx5fohz6nz4KU/NXVVRvxSD+cTiBFFqy3PeFJwy97uysP2ULMn/bl7IM2wglOn5wFaVIbMgYqEGFCQ2FfdBxTA+oqSJUO8eSMJabXdT3Nd108UTguUpAqzTizJTGwLEGqNNsuaZwwqxsMOZ7jWidI6461zWOlfwvS8pJ8nSCFnWZKEaDRzi1IKy1rpQeaCIqYIYRcFKO03SrxJZFa12fHuFe13nSWSifaMV+UlzEkMojHWadfg+uQXFU/O6sM2MOs+p3Vx89KYx3Hm/Boax99FOaTFKQSmmkjpYKiAJW/VIBEQVonJgkn4Rr9xfCzzubmMf4033VxdRGkGtxzM6RxsFe6EqDyH9Nc5Ayp0muz5EyySV1UdQx1ojPaQZs8tfI7YUEqu0JU5gRpjqMEqPxr9tQzpDlaq9uHmMzd7ygxqWMSnupf47KqHSuOWYJldaUtSiFZNUuFwIgPdyn/lI/y82M99vO6PK/xBoFWFf8qy9k2rVw/y75YFvrcaA+5PhyGEuswgVc67rfN2zr853h0sY+Yd2wFG+qTm6QgxSjpwKjQ6KIAjaIxNnj8q2MgjjpHOHWU6iDwr31pvHVxLftYFIc5MakBXGJS+dFAnl4W1TYDfBSb+Ff8MU38nCEGlMiSlzTKpnWBv5zfKkEqW6POow0svEg9EKRtyqQ2lBMHsilsLnXYjmxRYhI/2A77Nfuebqf2peOKX2myH7+y3y1fwvI9pMK1lCXtkEEy52QvEiAIE/Wj6VJ+0ngUR87mUr+r2kYwIqRyLhUc+KFsKjus6F+iqCA+8cBfOsbl0unjvlw/y74oSClbLGuu3gkjP7lbO/pY9lyecjy62IfihlXVlQT5WceyXlGtI0crSFPigcYcXTRwxGkUE9FvVXjFFeNRY0iX8tuHpQZjDfRaMrhHAaD9LBm45dLwqVDQ4E84/EanWVaOReEa/fRpPe0Y4olLWsfaXuoZeXzoJj4FvoBPhy6Te04cRDuJtoYNRjuJx6I9peGjPUmQxrDRTuMsa2nbsz4PGlnH9fAWAw2Gy+TouE3ABExgLAQmKUipPM2GdqlIDTRLnfHqkjGHWTqBVJAuPcEVJIBwplyrdDlBusr0V5GW+olVpOU0TMAETGDoBCYrSDUgMpvZxnUN1yYN++0vAQvSxdSN2hHLsToL0rHWrMtlAiawDAKTFaTA1KX3poOiLs/Gy/fLqBTH2V8CFqSLqRsL0sVwdCwmYAImMBYCkxakqkQuWTa5/M5l/qbiVXF7OS4CmvXS/aFDtQcJQpWDcq3SrTv9ZZZVTLVcZlqO2wRMwATGQsCCdCw16XKYgAmYgAmYgAmYwEAJWJAOtOKcbRMwARMwARMwARMYCwEL0rHUpMthAiZgAiZgAiZgAgMlYEE60Ipztk3ABEzABEzABExgLAQsSMdSky6HCZiACZiACZiACQyUgAXpQCvO2TYBEzABEzABEzCBsRCwIB1LTbocJmACJmACJmACJjBQAhakA604Z9sETMAETMAETMAExkLAgnQsNelymIAJmIAJmIAJmMBACViQDrTinG0TMAETMAETMAETGAsBC9Kx1KTLYQImYAImYAImYAIDJWBBOtCKc7ZNwARMwARMwARMYCwELEjHUpMuhwmYgAmYgAmYgAkMlIAF6UArztk2ARMwARMwARMwgbEQsCAdS026HCZgAiZgAiZgAiYwUAIWpAOtOGfbBEzABEzABEzABMZCwIJ0LDXpcpiACZiACZiACZjAQAlYkA604pxtEzABEzABEzABExgLAQvSsdSky2ECJmACJmACJmACAyVgQTqginv44YcHlNvlZXWdHI4ePVps27Zt83fzzTcvr6CZmCl7TD9lcfDgweK1117LhFzMrlnpLyaVYccyixE2xG/KDht9/PHHi6uvvrpIbVhc3nzzzeKcc87ZYu+HDx/W4colbTK2kfvuu2+LX9rIJZdcUvoh/VXVxUsvvVSQF9KelSZ8KPssfxQMJirP3XffXcAtOrbFhDgpfx9drBfKU2UXMe8wpQ6pb8JgU6nDj8rPku0+uln20YUP9hbbQlzXONEl3mXxm7wgxehpxGrQVBjbOUfFYdBNXKz43HpVGmo4hJHBKL0mDVR+2yz/4/H/Umz7h1uzv//8+jPZ/fj/b2/+jzbJtPK7Dg5NMsgAQd3EgYK6zNVx3HdG3BddVBTbtp35u+eeovjEJ87cj989ezajUT5Sm8BGU7vZDLSAFdKjXNFd8F8/n7WRL7z4aPHR576SPfap578Wo+jnel09UBe5+iPMKVdVR+yP9iP/U1rGPje1YXHAlmMbQkzNcth+DMN6FCCIN+LRPgRM6mdWGl2PI5xIm/Rm1b/6v1n+OE6c8gfXdIxiH1wQphIo8t+1LIsOR73ARYKS+qFc2ECVo0zRj1goDsLppEb7iI8wqWivSmOV++vsAz60E/LNT/1wVdtRvqOuga9+pIXrGq/iX/Ry68iy6Nh7Hh+VxU9OlUUDrnIyhCaDPg0kF6c6G47FjiHtgNOOZZbxpXkm7jZhEAkSpgjR6BAXOoaAXbSLAmXRHBaZV9VprDfFHxu/9sWynGFX//zPp0VNEDIKuyl4EK+JUz7S+iW9JrYZo0vtLB5L12X/6X5OTmQfiNDU6RjiddEOe0ztdaFpSHhm6qGIJxZJolV1xP6c/STBR79ZxUcFpz21tWXaGG2gyhFnehz7b9MGquJusl/tp67+EU+a9avzR3qUJ84AS4CpjAiOVHwx7kigNcnzKvzs2bOnLHNMi3LV1Qt1nfap8I2Ck+MSX4qbONNwOrbuZZV95OqLclDWKoeop5xp/bNP8WkZ45gVb/S76PXJClKg05ijy4nHeFzrhMXvLKcOF79pA1AcHFOnSyeiPLBUHuM+ravDqcsD6WPgTd26BKlm0pTPHAf4qexxmXJVHMtaqk5zAwX2pLzF9GN5ttTHggSp8qS04zLmo2odO2vq1GGm/tcpSBG7fRektPFYL3Fd7T9lOvZt2e2WNnGq0Goz2GaTvo5gYowAIc50IGaAhnvadhmU2Z/6XwZ/tZ80D0qLMlBmzRhW+cN/VXkQd/xyjvgRMX2zOfXvMV+UISeYVC7KkdqOmMAPl/NDnHVCTvGvYznLPmKe5Dfui+uwyDnKXmfrs+LNxbmofbNV1aJS6lE86uxSY9YgMUvkqCNt6o94U7+KIz1GZ6R8xMYJvjS/s5CSRpsw6xCkmnlNZ9UWyWEWpzbHVW8sU1clSPGXPbYgQRrzgW2ndhOP59Zh3dRVdVbrEqSaee27II18sZ2c/UQ/U1hXW8r1UbH90x8iMusGUXjJNtV/MvDGQVnpSayIsfavok6Ux6q0KDd5bpInjWMpF9LICS78wzEyEYN1L+mzyLPyR17TMTPNI/UcZ4d1nP0wIE7Wq+q7jxxm2YfKyJKyV514RH9xHRazwnSJN6Yxz/okBanEQTpwqyOjIcQOMdd5VMURK0OdCvHmGpfSI64mDmNt40i/TZiugjS9BzVefie/MV4EhMRnup9jadhceduUKRc+t4846QRnOdVpnU1Qr6mj/lXfm2EtSEtM6T2o8d7kKHSj+Mzt53gMm9ZB521fsu+Mri6g2lJVe6Z/pk2qr501kJIW4oxBV/03YSXYJFDSvpg0aJurECiUlbQ2+4AAiJk7zQiKTc6fgigubWuZ2y8epI3gEBOF6cOSsiJK+aV1lMsfdZuOnapjOFYxrNqfS2PV+1R3dfWuPFH2Jv7knyVtaNY41yXemMY862eOnPPENoCwMkYaZurYpx/+1FGxLxWvauB1lRvTyjUwpcWyicNY65zyFOPNrVfFkROIEgFxGe8hlRiVyEy3mbkirMKwLb+sS4xoX1Xe4v5ZHKLfput00Jydz2rgqtOcPxqyeKfpRkG6aTNRkEr05JaZexeVj5QFcae2GvOicMpn1TKNV3GwnzCpqxKI0W5YT+8hVf1rhjPdxi5iGLbxy0+2RrwKn+areOqp0/fp5thqH/6qnPzMWibhxTplyX5+U3dVfFIutE31bXW2nYZDeGGrm+2tKDbj0T5EKHHnZhTT+BaxrfaT1j/lioJbbFJ/MQ+KK+5jvWq/0oAJbPrmqAv6SfrhtN5yeVU5NbZSPtU5cVUxrNqfS2PV+1SmunonTwjutnVIO5pl513iXSSjM0eWRcbew7joiDD29MyKrLKfnww87sNQopPAiH7jcdZl+Gmc8qf0WC7DkX6a77p0oiBNB3hdWo/ikrgkIDiOi8IkFQ25tBW+jSDNxbOIfaovzVLk4pQflqmbS5Au6KGmNE9NthmQmzp1mKn/WO+5upQwjeIyCkrFJxtUHLIP2Zf8sYzhU3uN/uZelxDNnBh0eahp7vyMJAK1pSZ9FGKDfjLX7upw0CZj/AzK6rsZnDmGAKrrx+vib3tM7SctB2KUMsqJTepPx1nST+XGDtKoEx6rFOAxv3XrCEjqivqJdZRebk/jUFnhQB3y09hOnDmbEVuO981V2UfMJ/nuYq9on7pwXeONeZt3fTlKaN5cLTG8KlxGG5PCeGXY2p/bxzEqlmN1g7kMP40zjTuXF/mZZ0n6lLepkxjIzTjlBGkUIZoBjfskIhAXEiSkEZ0EhwRIPDbPuuqt61IzKGkeVKcsU0c9Kr30mOyF45th4wzpBAWp7C2KVO3DXnAITdkOS+xLzoJUJIa5VFtq2kfRvqJoa1Jq2l1VWya88tA23iZp5/xo/NnsA0Ie1Hfklrm4qgQXY1KcbU3Dkoc6wZr6X8U2+U3HUva1GRs1AxjrWycdsQx9LL/yl7MPHWNJGeHEsq0jXJXAnyfetvmo829BGuioI4hnEbl9BJHASBtRiG6zsyOOGCd+1BHmjsU45lknDQy8qYtiIJ1xmkeQkn4UD1GALEuQNi1z9EdjpQOLHVo8zrrqLQ4o8lMnSLPHLEhLsRntIdqguLKUnSBKdfITbSq11xh27nXPkM6NMBeB2lKTPkoDZi6eun11gzeCjnZZ197r4u5ybJbgUJxik+tn5Icl+Y/84DSrD+NSbzoexTjXsU49pWOp+uMm+ZF9pOViO42X7dRfkzRW4afOPigj+WYphw03uXTPCRe2knPzxJuLb559kxOkdD6IwFzl5MSn9qUdA4YxS0yqU8n5U3iOLevsnPRjZzXLUKIYSAf4nCAlPs1eSSTEGdI0DvxLWOiYZk8XPUM6q6zpcRqlnvBMj8Vt1WlqD/jBpmQvuTAc21IfExeksqmcIM3ZgwSojmFDsj/ZU+S+sHUL0oWhjBEhOGgT6YBKf0g70cDLoIuIYBkd+2izcoSRH+Kgj82JTfzgd5ZwU7yLXFJWylw1U6W0cv2M9sWw7KMclEnCIjJhlpFt9VcSecsac5T/tkvqAy66XYr8kW/2y6X1zX78Ucf0vdR36mAS65n42e5b+ZXvKvugfuEBo/QnG8/Zh+Kl3Gk741iTeBXHKpaTE6QYoio0Baz9GD5O4lXb0T/78B8bTDzOugwEf7GxqPGxXx1FGnYd210EaSoS0m2EggQEZZII0aVXjiEqWOJXwnbV5adOYkdflb7qNFdvOUEa7S3aQBl/TwRpVVlz+2W76bF4IhLrW/4kHKP45Fh6gpJuyy5iPNgpLhWk2i+/C1takC4MpSJS/6k+l6UcbUZtCfFAu5E4lR+WxBHFV4wTIcZgmzrSUZyrFiWxrKyT3yqX62e0L+2nJMiIM2XFMcrLMYm2HMuqfKxyP32L6p0l29FV1Td1neuPFTaKLuLI2YX8rnNZZR/Yqeow9cO26rPKPigT7SQtd9N4V8nkdC+wylTXnJaMPu2QqFxc7NiqOo2qOFS0nOHEfWljU7h1LCUiJRriMg76cT/rEpVp+CgMCB+FLuHYJzdLyMhfX5Zq9LEDZBCIdZuuYytnuPiFHwkelnN+OvSMdBa8IydIJSJT++DkQycc6bFoI2l42RVZx1+MIxW70baiXS2k2NzXG+tG67x0fI5Phy4kb47EBEzABEZGYJKCVDOfXUWhRMkZM14jMw4X50wCqvsoSM/0tfw9ykdXG+6aw5wg7RrX2MOtq47GztXlMwETGCeBSQpSqlKzoF2qdZ6wXdJzmP4QkMiwIO1PnfQ1J7KVVZ809JWH82UCJmACdQQmK0iBwqXUqkvyVdB0eTa93F/l3/vHRUAiw4J0XPW6jNLIVixIl0HXcZqACYyNwKQFKZXJYNH00juX+tsK2LEZzNTLI5Gh+0RXbQ+6ZK70Vy121p3+EOzPjIZQS86jCZhA3whMXpD2rUKcHxMwARMwARMwAROYGgEL0qnVuMtrAiZgAiZgAiZgAj0jYEHaswpxdkzABEzABEzABExgagQsSKdW4y6vCZiACZiACZiACfSMgAVpzyrE2TEBEzABEzABEzCBqRGwIJ1ajbu8JmACJmACJmACJtAzAhakPasQZ8cETMAETMAETMAEpkbAgnRqNe7ymoAJmIAJmIAJmEDPCFiQ9qxCnB0TMAETMAETMAETmBoBC9Kp1bjLawImYAImYAImYAI9I2BB2rMKcXZMwARMwARMwARMYGoELEinVuMurwmYgAmYgAmYgAn0jIAFac8qxNkxARMwARMwARMwgakRsCCdWo27vCZgAiZgAiZgAibQMwL/P/XHysmnVCpZAAAAAElFTkSuQmCC\"\u003e\u003cbr\u003e\u003c/p\u003e\n\u003cp\u003e\u003cem\u003e\u003csup\u003ea\u003c/sup\u003e\u003c/em\u003eEnergies in kcal mol\u003csup\u003e−\u003c/sup\u003e\u003csup\u003e1\u003c/sup\u003e, calculated at B3LYP-D3/Def2-TZVP//B3LYP-D3/Def2-SVP level of theory.\u003c/p\u003e\n\u003cp\u003eThe kinetic aspect of the hydrogen atom abstraction in the degradation of MR-TADF dopants was investigated by locating the key transition states on the potential energy surface. As illustrated in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e, we conceptualize the reaction as a sequential process, delineating the intermolecular HAT followed by the subsequent intramolecular cyclization. Initially, the radical cation of the hole-transporting host (\u003cstrong\u003eHost\u003c/strong\u003e\u003csup\u003e•+\u003c/sup\u003e) abstracts a hydrogen atom of the radical cation of the dopants (\u003cstrong\u003eD\u003c/strong\u003e\u003csup\u003e•+\u003c/sup\u003e), forming an open-shell intermediate \u003cstrong\u003e[D − H]\u003c/strong\u003e\u003csup\u003e\u003cstrong\u003e+\u003c/strong\u003e\u003c/sup\u003e\u003csub\u003e\u003cstrong\u003eos\u003c/strong\u003e\u003c/sub\u003e. This initial step is energetically demanding, primarily because the unpaired electron in \u003cstrong\u003e[D – H]\u003c/strong\u003e\u003csup\u003e\u003cstrong\u003e+\u003c/strong\u003e\u003c/sup\u003e\u003csub\u003e\u003cstrong\u003eos\u003c/strong\u003e\u003c/sub\u003e is localized on a carbon atom. However, the subsequent cyclization step provides the necessary thermodynamic driving force, spreading the spin density across the molecule through π-conjugation and leading to a stable structure. The cyclization phase reaches a critical point at the transition state (\u003cstrong\u003eTS\u003c/strong\u003e), identified by the formation of a new C–C bond.\u003c/p\u003e\n\u003cp\u003eOur analysis reveals a consistent energetic cost for the initial HAT across compounds \u003cstrong\u003e1\u003c/strong\u003e–\u003cstrong\u003e4\u003c/strong\u003e, averaging around 57 kcal mol\u003csup\u003e−1\u003c/sup\u003e, as enumerated in Table\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e, indicating that the variance in dopant reactivity does not stem from the energy required to cleave the C–H bond. Instead, it is the activation energies for the cyclization that determines the differences in dopant reactivity. The step barrier of the cyclization (ΔG\u003csup\u003e‡\u003c/sup\u003e\u003csub\u003ecyc\u003c/sub\u003e), representing the energy ascent to reach \u003cstrong\u003eTS\u003c/strong\u003e from the intermediate \u003cstrong\u003e[D – H]\u003c/strong\u003e\u003csup\u003e\u003cstrong\u003e+\u003c/strong\u003e\u003c/sup\u003e\u003csub\u003e\u003cstrong\u003eos\u003c/strong\u003e\u003c/sub\u003e, varies among the dopants, being highest for \u003cstrong\u003e2\u003c/strong\u003e (8.2 kcal mol\u003csup\u003e− 1\u003c/sup\u003e), followed by \u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e3\u003c/strong\u003e (6.4 and 6.1 kcal mol\u003csup\u003e− 1\u003c/sup\u003e), and lowest for \u003cstrong\u003e4\u003c/strong\u003e (4.9 kcal mol\u003csup\u003e− 1\u003c/sup\u003e). This pattern suggests that the extent of π-conjugation achieved through cyclization significantly influences reactivity, with compound \u003cstrong\u003e4\u003c/strong\u003e, possessing the smallest π-system, achieving the greatest stabilization post-cyclization, in contrast to compound \u003cstrong\u003e2\u003c/strong\u003e, which has a larger π-cloud and thus gains less energy from cyclization. The spin density distributions before and after cyclization are illustrated in Supplementary Fig.\u0026nbsp;10.\u003c/p\u003e\n\u003cdiv class=\"gridtable\"\u003e\n \u003ctable id=\"Tab4\" border=\"1\"\u003e\n \u003ccaption\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 4\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eEnergy components of the hydrogen atom abstraction of MR-TADF dopants 1–4.\u003csup\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eenergy (kcal mol\u003csup\u003e− 1\u003c/sup\u003e)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e1\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e2\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e3\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e4\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eΔ\u003cem\u003eG\u003c/em\u003e\u003csub\u003eHAT\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e57.21\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e57.48\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e57.28\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e56.88\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eΔ\u003cem\u003eG\u003c/em\u003e\u003csup\u003e‡\u003c/sup\u003e\u003csub\u003ecyc\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e6.36\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e8.17\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e6.08\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e4.91\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003ctfoot\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"5\"\u003e\u003csup\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sup\u003eEnergies calculated at B3LYP-D3/Def2-TZVP//B3LYP-D3/Def2-SVP level of theory.\u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tfoot\u003e\n \u003c/table\u003e\n\u003c/div\u003e\n\u003cp\u003eThis kinetic analysis, coupled with the previously discussed charge carrier trapping within the dopants, elucidates the observed stability trends. Despite compound \u003cstrong\u003e2\u003c/strong\u003e having the highest hole concentration, its better-than-expected stability compared to compounds \u003cstrong\u003e3\u003c/strong\u003e and \u003cstrong\u003e4\u003c/strong\u003e can be attributed to its relatively large cyclization energy barrier. Between compounds \u003cstrong\u003e3\u003c/strong\u003e and \u003cstrong\u003e4\u003c/strong\u003e, both having similar hole concentrations, the compound \u003cstrong\u003e4\u003c/strong\u003e's lower stability is ascribed to its higher intrinsic reactivity due to a lower cyclization barrier. This comprehensive kinetic perspective reveals the nuanced interplay between structural features, electronic properties, and degradation pathways, offering a deeper understanding of MR-TADF dopant stability.\u003c/p\u003e\n\u003cp\u003eFinally, we investigated the deleterious effect of the degradation byproduct on the operational stability of devices. The photoluminescence spectrum of compound \u003cstrong\u003e4′\u003c/strong\u003e shows a minor bathochromic shift of 30 nm compared to that of \u003cstrong\u003e4\u003c/strong\u003e, as depicted in Supplementary Fig.\u0026nbsp;11. Contrary to initial assumptions, the robust emission from compound \u003cstrong\u003e4′\u003c/strong\u003e disputes the notion that it would impair device performance by quenching excitons or acting as a nonradiative charge carrier recombination center. This is further supported by the unaltered electroluminescence spectra between pristine devices and those operated up to the \u003cem\u003eLT\u003c/em\u003e\u003csub\u003e80\u003c/sub\u003e and \u003cem\u003eLT\u003c/em\u003e\u003csub\u003e50\u003c/sub\u003e benchmarks for compounds \u003cstrong\u003e1\u003c/strong\u003e − \u003cstrong\u003e4\u003c/strong\u003e, represented in Supplementary Fig.\u0026nbsp;12. Such consistency in emission profiles suggests that the luminescent pathways of compound \u003cstrong\u003e4′\u003c/strong\u003e do not contribute to device deterioration. However, a notable gradual decrease in current density was observed over operational time, indicating poor current performance in devices incorporating compounds \u003cstrong\u003e1 − 4\u003c/strong\u003e when assessed at their respective \u003cem\u003eLT\u003c/em\u003e\u003csub\u003e80\u003c/sub\u003e and \u003cem\u003eLT\u003c/em\u003e\u003csub\u003e50\u003c/sub\u003e durations (Supplementary Fig.\u0026nbsp;13). This decline in current levels correspondingly led to diminished luminance, power efficiency, and \u003cem\u003eEQE\u003c/em\u003e, as detailed in Supplementary Table\u0026nbsp;3 and Fig.\u0026nbsp;14 − 16. These findings collectively hint at the formation of charge carrier traps within the cyclized byproducts of MR-TADF dopants, a theory further supported by the steady increase in operational voltage over time (Supplementary Fig.\u0026nbsp;17). In fact, \u003cstrong\u003e4′\u003c/strong\u003e has the HOMO shallower than that of \u003cstrong\u003e4\u003c/strong\u003e, supporting this notion (Supplementary Fig.\u0026nbsp;4). Although we are cautious to draw direct proportionalities, we find rough correlations between the voltage rise and the \u003cem\u003eLT\u003c/em\u003e\u003csub\u003e95\u003c/sub\u003e values and the Faradaic yield values (Supplementary Fig.\u0026nbsp;18).\u003c/p\u003e\n\u003ch3\u003eDeuteration effect\u003c/h3\u003e\n\u003cp\u003eDeuteration has recently been demonstrated to be a viable strategy for improving the operational stability of hosts,\u003csup\u003e38–41\u003c/sup\u003e and phosphorescent\u003csup\u003e42–45\u003c/sup\u003e and dipolar TADF emitters.\u003csup\u003e46,47\u003c/sup\u003e However, the specific mechanism by which deuterium confers protective benefits to OLED materials has not been fully elucidated. Our study suggests that the enhanced stability results from the substitution of C − H bonds with C − D bonds within the radical cation, considering our degradation mechanism centers on heterobimolecular HAT via homolytic cleavage of the C − H bond.\u003c/p\u003e\n\u003cp\u003eTo test this hypothesis and validate our proposed mechanism, we compared the intrinsic stability of a deuterated version of compound \u003cstrong\u003e1\u003c/strong\u003e, denoted as \u003cstrong\u003e1D\u003c/strong\u003e, with its protiated form, utilizing oxidative bulk electrolysis techniques. Compound \u003cstrong\u003e1\u003c/strong\u003e, chosen for its superior polaronic stability as indicated by its Faradaic yield, served as a model for this investigation. Our results unambiguously demonstrate the enhanced longevity of \u003cstrong\u003e1D\u003c/strong\u003e, with its oxidative degradation Faradaic yield being 30%, approximately 7% lower than that of compound \u003cstrong\u003e1\u003c/strong\u003e (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003ea and b). This finding aligns with our quantum chemical calculations, reinforcing the premise that intermolecular hydrogen atom abstraction constitutes the primary degradation pathway.\u003c/p\u003e\n\u003cp\u003eFurther comparative studies were conducted on multilayer OLEDs fabricated with the identical configuration as used previously, substituting \u003cstrong\u003e1\u003c/strong\u003e with \u003cstrong\u003e1D\u003c/strong\u003e. The key electroluminescence data are compiled in Supplementary Table\u0026nbsp;4. Unsurprisingly, the electroluminescence spectrum and the current density versus voltage profiles of the device incorporating \u003cstrong\u003e1D\u003c/strong\u003e closely mirrored those of the device based on compound \u003cstrong\u003e1\u003c/strong\u003e. Notably, a modest increase in the \u003cem\u003eEQE\u003c/em\u003e was observed for the \u003cstrong\u003e1D\u003c/strong\u003e-based device (24.0%) compared to the \u003cstrong\u003e1\u003c/strong\u003e-based device (23.1%) at a current density of 0.01 mA cm\u003csup\u003e−2\u003c/sup\u003e, while their roll-off profiles remained virtually identical (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003ee). Moreover, the operational lifetime experienced a notable improvement with the inclusion of \u003cstrong\u003e1D\u003c/strong\u003e, with the \u003cem\u003eLT\u003c/em\u003e\u003csub\u003e95\u003c/sub\u003e reaching approximately 4.3 hours, an increase of about 20% over the \u003cem\u003eLT\u003c/em\u003e\u003csub\u003e95\u003c/sub\u003e of the device based on compound \u003cstrong\u003e1\u003c/strong\u003e (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003ef). This analysis underscores the critical role of deuteration in mitigating degradation pathways through altering the dynamics of hydrogen atom abstraction, thus offering strong support for the proposed degradation mechanism.\u003c/p\u003e"},{"header":"Discussion","content":"\u003cp\u003eOrganic molecules that exhibit MR-TADF have become vital to the development of highly efficient OLEDs with saturated color purity. Despite their significance, research that closely examines the relationship between the operational lifetimes of OLEDs and the intrinsic stability of MR-TADF compounds is notably rare, even though the device longevity is crucial for commercial viability. In our study, we discovered that the operational lifetime of OLEDs is not directly linked to the excitonic stability of MR-TADF molecules \u003cb\u003e1\u003c/b\u003e\u0026thinsp;\u0026minus;\u0026thinsp;\u003cb\u003e4\u003c/b\u003e. Instead, our investigations, particularly through bulk electrolysis experiments, highlighted the pronounced instability of the one-electron oxidized forms of these molecules. We established a clear correlation between the Faradaic yield for oxidative degradation and the operational lifetime of the devices, identifying radical cations\u0026mdash;or positive polarons\u0026mdash;as the critical intermediates that dictate device longevity.\u003c/p\u003e \u003cp\u003eChemical analyses, encompassing mass spectrometry, \u003csup\u003e1\u003c/sup\u003eH NMR spectroscopy, and UV\u0026thinsp;\u0026minus;\u0026thinsp;Vis spectroelectrochemical measurements, have demonstrated the formation of a cyclization byproduct following hole trapping in the MR-TADF compounds. This conclusion is further supported by our independent synthesis of the cyclization byproduct (compound \u003cb\u003e4\u0026prime;\u003c/b\u003e). Quantum chemical calculations suggested that oxidative cyclization is the primary degradation pathway for the oxidized dopants. This process begins with hydrogen atom abstraction by another radical cation, specifically targeting the C\u0026ndash;H bond \u003cem\u003eortho\u003c/em\u003e to the nitrogen atom on the \u003cem\u003eN\u003c/em\u003e-aryl substituent. Subsequent intramolecular cyclization, driven by the need to achieve extended π-conjugation, leads to the irreversible C\u0026ndash;C bond formation.\u003c/p\u003e \u003cp\u003eOur findings offer a strategic approach to enhancing the stability of MR-TADF molecules for OLED applications: by reinforcing the C\u0026thinsp;\u0026minus;\u0026thinsp;H bond at electrochemically active sites, such as the \u003cem\u003eortho\u003c/em\u003e- and \u003cem\u003epara\u003c/em\u003e-positions relative to nitrogen atoms in the azaborine unit. This approach was empirically validated through the synthesis of a deuterated MR-TADF compound (\u003cb\u003e1D\u003c/b\u003e), which not only demonstrated a reduced Faradaic yield for oxidative degradation but also significantly extended the operational lifetime compared to its undeuterated counterpart.\u003c/p\u003e \u003cp\u003eThis research underscores the importance of managing electrochemical reactivity to ensure the high stability of MR-TADF molecules. Given the extensive body of existing research on the electrochemical behaviors of arylamine-based organic molecules,\u003csup\u003e48\u003c/sup\u003e we anticipate that the insights gained from our study, combined with existing knowledge, will pave the way for the design and development of highly stable MR-TADF molecules for electroluminescence applications.\u003c/p\u003e"},{"header":"Methods","content":"\u003cp\u003e \u003cb\u003eGeneral procedures.\u003c/b\u003e Chemicals were purchased from commercial suppliers, and used without further purification. \u003csup\u003e1\u003c/sup\u003eH and \u003csup\u003e13\u003c/sup\u003eC{\u003csup\u003e1\u003c/sup\u003eH} NMR spectra were recorded on a Bruker AVANCE III HD 500 spectrometer and a Bruker AVANCE III 600 spectrometer, with CD\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e as the solvent. Chemical shifts were referenced to the peaks corresponding to residual solvents. We examined the purity and mass spectra of materials by performing liquid chromatography mass spectrometer-ion trap-time of flight (LCMS-IT-TOF) analyses. The LCMS-IT-TOF instrumentation consisted of a Shimadzu LC-30A Nexera SR System instrument connected to a hybrid IT-TOF mass spectrometer equipped with an ESI source. Compound \u003cb\u003e2\u003c/b\u003e was prepared following the method of Kondo \u003cem\u003eet al\u003c/em\u003e.\u003csup\u003e10\u003c/sup\u003e Compound \u003cb\u003e4\u003c/b\u003e was prepared following the method of Han \u003cem\u003eet al\u003c/em\u003e.\u003csup\u003e31\u003c/sup\u003e Organic materials for device fabrication were purchased from commercial suppliers and were purified by sublimation at 10\u003csup\u003e\u0026minus;\u0026thinsp;5\u003c/sup\u003e torr prior to deposition. PMMA (Mw\u0026thinsp;~\u0026thinsp;120,000, Sigma\u0026minus;Aldrich) films doped with the MR-TADF dopants (2 wt %) were dissolved in 1,2-dichoroethane (5 wt % total solute relative to solution). The solution was sonicated for 30 min, and passed through a membrane filter (pore size\u0026thinsp;=\u0026thinsp;8.0 \u0026micro;m). An aliquot of the polymer solution was placed on a pre-cleaned glass substrate and was spin-cast using an EPLEX, SPIN-1200D spin coater. Spectrophotometric-grade THF stored under an inert atmosphere was used for spectroscopic and electrochemical measurements.\u003c/p\u003e \u003cp\u003e \u003cb\u003eSynthesis of 1.\u003c/b\u003e A \u003cem\u003etert\u003c/em\u003e-butyllithium solution (1.7 M in pentane, 8.50 mL, 14.5 mmol) was added dropwise to a stirred solution of \u003cem\u003eN\u003c/em\u003e\u003csup\u003e\u003cem\u003e1\u003c/em\u003e\u003c/sup\u003e,\u003cem\u003eN\u003c/em\u003e\u003csup\u003e\u003cem\u003e1\u003c/em\u003e\u003c/sup\u003e,\u003cem\u003eN\u003c/em\u003e\u003csup\u003e\u003cem\u003e3\u003c/em\u003e\u003c/sup\u003e,\u003cem\u003eN\u003c/em\u003e\u003csup\u003e\u003cem\u003e3\u003c/em\u003e\u003c/sup\u003e-tetra([1,1'-biphenyl]-4-yl)-2-chlorobenzene-1,3-diamine (5.19 g, 6.90 mmol) in \u003cem\u003etert\u003c/em\u003e-butylbenzene (70 mL) at 0 ℃ under a N\u003csub\u003e2\u003c/sub\u003e atmosphere. The resulting mixture was heated to 60 ℃ and stirred for an hour. The solution was cooled to \u0026minus;78 ℃, and boron tribromide (1.40 mL, 14.5 mmol) was slowly added. The resultant mixture was stirred for 2 h at 0 ℃. After additional stirring, diisopropylethylamine (2.40 mL, 13.8 mmol) was added to the reaction mixture at 0 ℃ and then the reaction mixture was heated to 110 ℃ and stirred for 3 h. The resultant mixture was cooled to 0 ℃ and then carefully quenched with saturated aq. NaHCO\u003csub\u003e3\u003c/sub\u003e solution. Extraction was performed with dichloromethane; the collected organic layer was dried over MgSO\u003csub\u003e4\u003c/sub\u003e, filtered, and concentrated \u003cem\u003ein vacuo\u003c/em\u003e. The crude mixture was purified by column chromatography on silica gel. The obtained product was recrystallized from dichloromethane/hexane/methanol to give \u003cb\u003e1\u003c/b\u003e as a yellow solid (2.24 g, 45%). \u003csup\u003e\u003cb\u003e1\u003c/b\u003e\u003c/sup\u003e\u003cb\u003eH NMR\u003c/b\u003e (500 MHz, CD\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e): \u003cem\u003eδ\u003c/em\u003e 9.39 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;2.0 Hz, 2H), 7.97 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;8.5 Hz, 4H), 7.84 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;8.0 Hz, 4H), 7.77 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;8.0 Hz, 6H), 7.48\u0026minus;7.55 (m, 12H), 7.44 (t, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;8.0 Hz, 2H), 7.36 (t, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;7.5 Hz, 2H), 7.34 (t, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;8.5 Hz, 1H), 7.00 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;9.0 Hz, 2H), 6.32 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;8.0 Hz, 2H). \u003csup\u003e\u003cb\u003e13\u003c/b\u003e\u003c/sup\u003e\u003cb\u003eC{\u003c/b\u003e\u003csup\u003e\u003cb\u003e1\u003c/b\u003e\u003c/sup\u003e\u003cb\u003eH} NMR\u003c/b\u003e (125 MHz, CD\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e): \u003cem\u003eδ\u003c/em\u003e 147.16, 146.83, 141.62, 141.29, 141.16, 140.13, 133.32, 132.37, 132.22, 130.73, 129.80, 128.91, 127.83, 127.20, 126.77, 126.73, 117.75, 105.60. \u003cb\u003eMS\u003c/b\u003e (ESI): \u003cem\u003em\u003c/em\u003e/\u003cem\u003ez\u003c/em\u003e calculated for C\u003csub\u003e54\u003c/sub\u003eH\u003csub\u003e38\u003c/sub\u003eBN\u003csub\u003e2\u003c/sub\u003e [M\u0026thinsp;+\u0026thinsp;H]\u003csup\u003e+\u003c/sup\u003e: 725.312, Found: 725.302.\u003c/p\u003e \u003cp\u003e \u003cb\u003eSynthesis of 3.\u003c/b\u003e The full synthetic details are described in Supplementary Method 1. A \u003cem\u003etert\u003c/em\u003e-butyllithium solution (1.7 M in pentane, 8.50 mL, 14.5 mmol) was added dropsie to a stirred solution of \u003cem\u003eN\u003c/em\u003e\u003csup\u003e\u003cem\u003e5\u003c/em\u003e\u003c/sup\u003e-([1,1'-biphenyl]-2-yl)-\u003cem\u003eN\u003c/em\u003e\u003csup\u003e\u003cem\u003e1\u003c/em\u003e\u003c/sup\u003e,\u003cem\u003eN\u003c/em\u003e\u003csup\u003e\u003cem\u003e1\u003c/em\u003e\u003c/sup\u003e,\u003cem\u003eN\u003c/em\u003e\u003csup\u003e\u003cem\u003e3\u003c/em\u003e\u003c/sup\u003e,\u003cem\u003eN\u003c/em\u003e\u003csup\u003e\u003cem\u003e3\u003c/em\u003e\u003c/sup\u003e,\u003cem\u003eN\u003c/em\u003e\u003csup\u003e\u003cem\u003e5\u003c/em\u003e\u003c/sup\u003e-penta([1,1'-biphenyl]-4-yl)-2-chlorobenzene-1,3,5-triamine (6.19 g, 5.78 mmol) in \u003cem\u003etert\u003c/em\u003e-butylbenzene (100 mL) at 0 ℃ under an N\u003csub\u003e2\u003c/sub\u003e atmosphere. The resultant mixture was heated to 60 ℃ and stirred for 2 h. The solution was then cooled to \u0026minus;78 ℃, and boron tribromide (1.40 mL, 14.5 mmol) was slowly added. The resultant mixture was stirred for an hour at 0 ℃. After additional stirring, diisopropylethylamine (2.50 mL, 14.3 mmol) was added to the reaction mixture at 0 ℃, then the reaction mixture was heated to 110 ℃ and stirred for 3 h before being cooled to 0 ℃ and carefully quenched with saturated aq. NaHCO\u003csub\u003e3\u003c/sub\u003e solution. The crude product was then extracted with dichloromethane, and the collected organic layer was dried over MgSO\u003csub\u003e4\u003c/sub\u003e, filtered, and concentrated \u003cem\u003ein vacuo\u003c/em\u003e. The crude mixture was purified by column chromatography on silica gel. Then the obtained product was suspended to ethyl acetate. The suspension was heated to 80 ℃ and stirred for an hour. The insoluble solid was collected by filtration to give \u003cb\u003e3\u003c/b\u003e as a yellow solid (1.8 g, 30%). \u003csup\u003e\u003cb\u003e1\u003c/b\u003e\u003c/sup\u003e\u003cb\u003eH NMR\u003c/b\u003e (600 MHz, CD\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e): \u003cem\u003eδ\u003c/em\u003e 9.33 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;2.4 Hz, 2H), 7.82 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;8.4 Hz, 4H), 7.75 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;8.4 Hz, 4H), 7.71 (dd, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;9.0 Hz, 2.4 Hz, 2H), 7.56 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;6.6 Hz, 4H), 7.50 (t, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;8.0 Hz, 4H), 7.33\u0026ndash;7.42 (m, 11H), 7.27\u0026ndash;7.31 (m, 5H), 7.21\u0026ndash;7.24 (m, 1H), 7.14\u0026ndash;7.16 (m, 4H), 7.11\u0026ndash;7.14 (m, 1H), 7.04\u0026ndash;7.08 (m, 4H), 6.99 (dd, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;7.8 Hz, 2H), 6.97 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;8.4 Hz, 2H), 6.79 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;8.4 Hz, 2H), 5.63 (s, 2H). \u003cb\u003eMS\u003c/b\u003e (ESI): \u003cem\u003em\u003c/em\u003e/\u003cem\u003ez\u003c/em\u003e calculated for C\u003csub\u003e78\u003c/sub\u003eH\u003csub\u003e55\u003c/sub\u003eBN\u003csub\u003e3\u003c/sub\u003e [M\u0026thinsp;+\u0026thinsp;H]\u003csup\u003e+\u003c/sup\u003e: 1044.448, Found: 1044.452.\u003c/p\u003e \u003cp\u003e \u003cb\u003eSynthesis of 1D.\u003c/b\u003e The full synthetic details are described in Supplementary Method 2. A \u003cem\u003etert\u003c/em\u003e-butyllithium solution (1.7 M in pentane, 5.50 mL, 9.35 mmol) was added dropwise to a stirred solution of \u003cem\u003eN\u003c/em\u003e\u003csup\u003e\u003cem\u003e1\u003c/em\u003e\u003c/sup\u003e,\u003cem\u003eN\u003c/em\u003e\u003csup\u003e\u003cem\u003e1\u003c/em\u003e\u003c/sup\u003e,\u003cem\u003eN\u003c/em\u003e\u003csup\u003e\u003cem\u003e3\u003c/em\u003e\u003c/sup\u003e,\u003cem\u003eN\u003c/em\u003e\u003csup\u003e\u003cem\u003e3\u003c/em\u003e\u003c/sup\u003e-tetrakis([1,1'-biphenyl]-4-yl-\u003cem\u003ed\u003c/em\u003e\u003csub\u003e\u003cem\u003e9\u003c/em\u003e\u003c/sub\u003e)-2-chlorobenzene-1,3-diamine (3.50 g, 4.45 mmol) in \u003cem\u003etert\u003c/em\u003e-butylbenzene (90 mL) at 0 ℃ under an N\u003csub\u003e2\u003c/sub\u003e atmosphere. The resultant mixture was heated to 60 ℃ and stirred for an hour. The solution was cooled to \u0026minus;78 ℃ and boron tribromide (0.90 mL, 9.34 mmol) was slowly added. The resultant mixture was stirred for 2 h at 0 ℃. After additional stirring, diisopropylethylamine (1.60 mL, 9.15 mmol) was added to the reaction mixture at 0 ℃; the mixture was then heated to 110 ℃ and stirred for 3 h. The resultant mixture was cooled to 0 ℃ and carefully quenched with saturated aq. NaHCO\u003csub\u003e3\u003c/sub\u003e solution. The crude product was then extracted with dichloromethane, and the collected organic layer was dried over MgSO\u003csub\u003e4\u003c/sub\u003e, filtered, and concentrated \u003cem\u003ein vacuo\u003c/em\u003e. The crude mixture was purified by column chromatography on silica gel. Then the obtained product was recrystallized from dichloromethane/hexane/methanol to give \u003cb\u003e1D\u003c/b\u003e as a yellow solid (0.800 g, 24%). \u003csup\u003e\u003cb\u003e1\u003c/b\u003e\u003c/sup\u003e\u003cb\u003eH NMR\u003c/b\u003e (500 MHz, CD\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e): \u003cem\u003eδ\u003c/em\u003e 7.98 (s, 0.17H), 7.84 (s, 2.1H), 7.78 (s, 2.3H), 7.51\u0026ndash;7.55 (m, 1H), 7.44 (s, 0.3H), 7.37 (s, 0.28H), 7.35 (t, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;8.5 Hz, 1H), 6.99 (s, 0.4H), 6.32 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;8.5 Hz, 2H); deuterium is incorporated at ~\u0026thinsp;80%. \u003csup\u003e\u003cb\u003e13\u003c/b\u003e\u003c/sup\u003e\u003cb\u003eC{\u003c/b\u003e\u003csup\u003e\u003cb\u003e1\u003c/b\u003e\u003c/sup\u003e\u003cb\u003eH} NMR\u003c/b\u003e (125 MHz, CD\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e): \u003cem\u003eδ\u003c/em\u003e 147.11, 146.84, 141.17, 132.21, 127.07, 126.62, 105.56. \u003cb\u003eMS\u003c/b\u003e (ESI): \u003cem\u003em\u003c/em\u003e/\u003cem\u003ez\u003c/em\u003e calculated for C\u003csub\u003e54\u003c/sub\u003eH\u003csub\u003e10\u003c/sub\u003eD\u003csub\u003e27\u003c/sub\u003eBN\u003csub\u003e2\u003c/sub\u003e [M-7D\u0026thinsp;+\u0026thinsp;7H]\u003csup\u003e+\u003c/sup\u003e: 751.474, Found: 751.387.\u003c/p\u003e \u003cp\u003e \u003cb\u003eDevice fabrication and characterization.\u003c/b\u003e The organic layers were deposited consecutively onto pre-cleaned ITO glass substrates using a thermal evaporation system at a pressure less than 1.0 \u0026times; 10\u003csup\u003e\u0026minus;6\u003c/sup\u003e torr. A 1 nm-thick LiQ layer and a 100 nm-thick Al layer were deposited as a cathode via thermal evaporation. The deposition rates of the organic and metal layers were 0.1 nm s\u003csup\u003e\u0026minus;1\u003c/sup\u003e and 0.5 nm s\u003csup\u003e\u0026minus;1\u003c/sup\u003e, respectively. LiQ was deposited at a rate 0.01 nm s\u003csup\u003e\u0026minus;1\u003c/sup\u003e. The active device area of 4 mm\u003csup\u003e2\u003c/sup\u003e was defined by the area of overlap between the ITO and Al electrodes. The current, voltage, and luminance of the OLED devices were measured with a system comprising a Keithley 2400 Source-Meter and a Topcon SR-3AR spectroradiometer. Operational lifetime measurements of the devices were conducted in a constant-current mode. Current\u0026minus;voltage characteristics of single-carrier devices with the device structure introduced in Supplementary Fig.\u0026nbsp;9 were measured with a system consisting of a Keithley 2400 source-meter. On the basis of the lack of emission under the given voltage, we inferred that only hole transport occurred within the single-carrier devices.\u003c/p\u003e \u003cp\u003e \u003cb\u003eSteady-state UV\u0026minus;Vis absorption measurements\u003c/b\u003e. UV\u0026minus;Vis absorption spectra were collected at 298 K using an Agilent Cary 300 spectrophotometer. Stock solutions with a concentration of 10 mM were prepared in THF. Sample solutions with a concentration of 10 \u0026micro;M in THF, which had been previously saturated with Ar, were prepared prior to the measurements by diluting the stock solution, unless otherwise stated. A total of 3.0 mL of each solution was added to a quartz cell (Hellma, beam path length\u0026thinsp;=\u0026thinsp;1.0 cm).\u003c/p\u003e \u003cp\u003e \u003cb\u003eSteady-state photoluminescence measurements\u003c/b\u003e. Photoluminescence spectra were obtained at 298 K by using a Photon Technology International Quanta Master 400 scanning spectrofluorometer. Samples for the measurements were prepared as 10 \u0026micro;M solutions in THF, unless otherwise stated. The solutions were deaerated by bubbling Ar gas for at least 10 min before the measurement. All operations were controlled with the FelixGX software provided by the manufacturer.\u003c/p\u003e \u003cp\u003e \u003cb\u003ePhotoluminescence lifetime measurements\u003c/b\u003e. PMMA films doped with (quartz substrate) 2 wt % \u003cb\u003e1\u0026minus;4\u003c/b\u003e were used for the determination of the photoluminescence lifetimes. Photoluminescence decay traces were acquired using time-correlated single-photon-counting techniques with a PicoQuant, FluoTime 200 instrument after picosecond pulsed laser excitation (pulse duration\u0026thinsp;=\u0026thinsp;2.5 ns). A diode laser that produced 377 nm pulses (PicoQuant, LDH375) was driven by a PDL800-D driver (PicoQuant). Transient photon signals were collected at \u003cem\u003eλ\u003c/em\u003e\u003csub\u003eobs\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;471 nm (\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e), 467 nm (\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e), 461 nm (\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e), and 459 nm (\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e). The burst mode was used to monitor delayed fluorescence. The fluorescence signals at the emission peak wavelengths of the compounds were obtained with an automated motorized monochromator. Photoluminescence decay profiles were analyzed (OriginPro 8.0, OriginLab) using a biexponential decay model. Temperature-dependent measurements were conducted in the temperature range 79\u0026minus;315 K using an Oxford Instruments Omicron Nanoscience, Optistat DN2 variable-temperature liquid N\u003csub\u003e2\u003c/sub\u003e cryostat equipped with a MercuryiTC temperature controller.\u003c/p\u003e \u003cp\u003e \u003cb\u003eElectrochemical characterization\u003c/b\u003e. Cyclic and differential pulse voltammetry experiments were conducted using a CH Instruments CHI630 B potentiostat in conjunction with a three-electrode cell assembly. A Pt wire and a glassy carbon disc were used as the counter and working electrodes, respectively. A Ag/AgNO\u003csub\u003e3\u003c/sub\u003e couple was used as the pseudo-reference electrode. Measurements were carried out in Ar-saturated THF (2.0 mL) with 0.10 M tetrabutylammonium hexafluorophosphate as the supporting electrolyte at scan rates of 100 mV s\u003csup\u003e\u0026minus;1\u003c/sup\u003e (cyclic voltammetry) and 4.0 mV s\u003csup\u003e\u0026minus;1\u003c/sup\u003e (differential pulse voltammetry). The ferrocenium/ferrocene couple was used as an external reference.\u003c/p\u003e \u003cp\u003e \u003cb\u003eSpectroelectrochemical measurements\u003c/b\u003e. UV\u0026minus;Vis absorption spectra of the radical species were acquired via the amperometric \u003cem\u003eI\u003c/em\u003e\u0026minus;\u003cem\u003et\u003c/em\u003e curve method using an Agilent Cary 300 spectrophotometer with anodic potentials applied. A blank spectrum was acquired for a 0.10 M tetrabutylammonium hexafluorophosphate solution (THF) in a spectroelectrochemical cell (path length\u0026thinsp;=\u0026thinsp;0.5 mm) equipped with a Pt mesh working electrode, a Pt wire counter electrode, and a Ag/AgNO\u003csub\u003e3\u003c/sub\u003e pseudo reference electrode. A 1.0 mM sample solution (500 \u0026micro;L) was delivered into the spectroelectrochemical cell for the measurement.\u003c/p\u003e \u003cp\u003e \u003cb\u003ePhotolysis.\u003c/b\u003e An Ar-saturated 25 mL THF solution containing 100 \u0026micro;M sample was placed in a 40 mL scintillation vial equipped with a Teflon-coated magnetic stir bar. The solution was photoirradiated using a monochromatic light source (450 nm) positioned 1 cm from the vial. Aliquots of the 100 \u0026micro;L reaction mixture were collected during the photolysis reaction and diluted with 50 \u0026micro;L of 1.0 mM of benzophenone in THF and 850 \u0026micro;L CH\u003csub\u003e3\u003c/sub\u003eCN for quantification of the residual concentration of the components. High-performance liquid chromatography (HPLC) experiments were performed on an Agilent 6120 DW LC/MSD instrument equipped with a Poroshell, EC-C18 column. The photolyzed solutions, diluted in HPLC grade CH\u003csub\u003e3\u003c/sub\u003eCN (1:4, v/v), were passed through a poly(vinylidene fluoride) (PVDF) membrane filter (pore size\u0026thinsp;=\u0026thinsp;8.0 \u0026micro;m) prior to injection. A 5 \u0026micro;L sample volume was injected and allowed to pass through the column at room temperature; a gradient eluent with increasing fractions of CH\u003csub\u003e3\u003c/sub\u003eCN in H\u003csub\u003e2\u003c/sub\u003eO was used. The quantum yields for photolysis (\u003cem\u003eΦ\u003c/em\u003e\u003csub\u003edeg\u003c/sub\u003e) were determined according to Eq.\u0026nbsp;1:\u003cdiv id=\"Equa\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equa\" name=\"EquationSource\"\u003e\n$${\\varPhi }_{\\text{d}\\text{e}\\text{g}}=\\frac{{k}_{\\text{o}\\text{b}\\text{s}}\\times V}{\\left(1-{10}^{-Abs}\\right)\\times q} \\left(\\text{e}\\text{q} 1\\right)$$\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003e,where \u003cem\u003ek\u003c/em\u003e\u003csub\u003eobs\u003c/sub\u003e represents the degradation rate corresponding to the slope of the linear fit of the initial five data points shown in Supplementary Fig.\u0026nbsp;6b, V is the volume of the solution (25 mL), 1 \u0026minus; 10\u003csup\u003e\u0026minus;\u003cem\u003eAbs\u003c/em\u003e\u003c/sup\u003e is the photokinetic factor based on the absorbance at a wavelength of 450 nm, and \u003cem\u003eq\u003c/em\u003e is the photon flux (4.0 \u0026times; 10\u003csup\u003e\u0026minus;8\u003c/sup\u003e einstein s\u003csup\u003e\u0026minus;1\u003c/sup\u003e) determined using standard ferrioxalate actinometry and additionally confirmed using an optical powermeter.\u003c/p\u003e \u003cp\u003e \u003cb\u003eOxidative bulk electrolysis.\u003c/b\u003e Oxidative bulk electrolysis experiments were conducted using 25 mL of Ar-saturated THF solutions containing 200 \u0026micro;M sample, along with 0.10 M tetrabutylammonium hexafluorophosphate, in a 40 mL scintillation vial equipped with a Teflon-coated magnetic stir bar. Oxidative bulk electrolysis was performed at potentials of 1.04 V vs SCE for \u003cb\u003e1\u003c/b\u003e and \u003cb\u003e3\u003c/b\u003e, 1.01 V vs SCE for \u003cb\u003e2\u003c/b\u003e, and 0.98 V vs SCE for \u003cb\u003e4\u003c/b\u003e. A Pt mesh and a Pt coil served as the working and counter electrodes, respectively. A Ag/AgNO\u003csub\u003e3\u003c/sub\u003e pseudo-reference electrode was used. Changes in the Faradaic charge transferred from the working electrode during oxidative bulk electrolysis were monitored. Aliquots of the 100 \u0026micro;L reaction mixture were collected during the electrolysis reaction and diluted with 50 \u0026micro;L of 1.0 mM benzophenone in THF and 850 \u0026micro;L CH\u003csub\u003e3\u003c/sub\u003eCN for quantification of the residual concentration of the components. HPLC experiments were performed on an Agilent 6120 DW LC/MSD instrument equipped with a Poroshell, EC-C18 column. The electrolyzed solutions, diluted in HPLC grade CH\u003csub\u003e3\u003c/sub\u003eCN (1:4, v/v), were passed through a PVDF membrane filter (pore size\u0026thinsp;=\u0026thinsp;8.0 \u0026micro;m) prior to injection. A 5 \u0026micro;L sample volume was injected and allowed to pass through the column at room temperature; a gradient eluent with increasing fractions of CH\u003csub\u003e3\u003c/sub\u003eCN in H\u003csub\u003e2\u003c/sub\u003eO was used. The Faradaic yield for oxidative bulk electrolysis was determined following Eq.\u0026nbsp;2:\u003cdiv id=\"Equb\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equb\" name=\"EquationSource\"\u003e\n$$\\text{F}\\text{a}\\text{r}\\text{a}\\text{d}\\text{a}\\text{i}\\text{c} \\text{y}\\text{i}\\text{e}\\text{l}\\text{d}=\\frac{{k}_{\\text{o}\\text{b}\\text{s}}\\times V\\times t}{C\\times F} \\left(\\text{e}\\text{q} 2\\right)$$\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003e,where \u003cem\u003ek\u003c/em\u003e\u003csub\u003eobs\u003c/sub\u003e is the degradation rate corresponding to the slope of the linear fit of the initial five data points shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb, V is the volume of the solution (25 mL), \u003cem\u003et\u003c/em\u003e is the reaction time, \u003cem\u003eC\u003c/em\u003e is the total charge transferred at time \u003cem\u003et\u003c/em\u003e, and \u003cem\u003eF\u003c/em\u003e is the Faraday constant.\u003c/p\u003e \u003cp\u003e \u003cb\u003eDegradation product analyses.\u003c/b\u003e ESI mass analyses were performed under positive-ion detection mode (voltage\u0026thinsp;=\u0026thinsp;70 V) in the range 200\u0026minus;1500 amu.\u003c/p\u003e \u003cp\u003e \u003cb\u003eCalculation methods.\u003c/b\u003e All density functional theory (DFT)\u003csup\u003e49\u003c/sup\u003e calculations were performed with the Orca 4.2 suite of quantum chemistry programs.\u003csup\u003e50\u003c/sup\u003e Geometries of intermediates and transition states were optimized with B3LYP\u003csup\u003e51,52\u003c/sup\u003e hybrid functional along with Grimme\u0026rsquo;s D3 dispersion\u003csup\u003e53\u003c/sup\u003e correction (B3LYP-D3) using the Ahlrichs balanced basis sets of split valence quality, Def2-SVP.\u003csup\u003e54\u003c/sup\u003e The RIJCOSX approximation\u003csup\u003e55,56\u003c/sup\u003e was employed using the Def2/J auxiliary basis set.\u003csup\u003e57\u003c/sup\u003e Single point calculations were carried out with the valence polarized triple-zeta quality Ahlrichs basis set, Def2-TZVP,\u003csup\u003e54\u003c/sup\u003e to obtain more reliable electronic energies. To evaluate the zero-point energy (ZPE) and entropy correction, the frequency calculations were performed at the same level of theory used in the geometry optimization. Because the dopant and HT host molecules are confined in the device in the solid phase, solvation correction was not included in evaluating the Gibbs free energies.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eData availability\u003c/h2\u003e\n\u003cp\u003eThe data that support the findings of this study are available from the corresponding author upon reasonable request.\u003c/p\u003e\n\u003ch2\u003eAcknowledgements\u003c/h2\u003e\n\u003cp\u003eThis work was supported by the Midcareer Research Program (RS-2023-00208856) through National Research Foundation grants funded by the Ministry of Science, Information, and Communication Technology (ICT) and Future Planning (MSIP), and by the Institute for Basic Science in Korea (IBS-R010-A1).\u003c/p\u003e\n\u003ch2\u003eAuthor Contributions\u003c/h2\u003e\n\u003cp\u003eB.H.J. performed the spectroscopic experiments, analyzed the data, and wrote the manuscript. H.S.K. synthesized and characterized the materials, and co-wrote the manuscript. J.K. fabricated and tested the devices. Y.P., E.L., H.M., and C.J. conducted and analyzed the quantum chemical calculations and Y.P. co-wrote the manuscript. Y.J. coordinated the material preparation and OLED experiments. S.C. performed the electrochemical experiments. M.-H.B. supervised the quantum chemical calculations at KAIST, and co-wrote the manuscript. Y.Y. coordinated all of the experiments and analyses, and co-wrote the manuscript. All authors contributed to discussion on the study, and edited the manuscript.\u003c/p\u003e\n\u003ch2\u003eAdditional information\u003c/h2\u003e\n\u003cp\u003eSupplementary information is available in the online version of the paper. Reprints and permissions information are available online at \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003e\u003ca href=\"https://doi.org:DOI\" target=\"_blank\"\u003ewww.nature.com/reprints\u003c/a\u003e\u003c/span\u003e\u003c/span\u003e. Correspondence and requests for materials should be addressed to Y.Y. ([email protected]).\u003c/p\u003e\n\u003ch2\u003eCompeting interests\u003c/h2\u003e\n\u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eBaranoff, E., Yum, J.-H., Graetzel, M. \u0026amp; Nazeeruddin, M. K. Cyclometallated iridium complexes for conversion of light into electricity and electricity into light. \u003cem\u003eJ. Organomet. Chem.\u003c/em\u003e \u003cstrong\u003e694\u003c/strong\u003e, 2661-2670 (2009).\u003c/li\u003e\n\u003cli\u003eLonghi, E. \u0026amp; De Cola, L. in \u003cem\u003eIridium (III) in Optoelectronic and Photonics Applications\u003c/em\u003e (ed Eli Zysman-Colman) 205-274 (John Wiley \u0026amp; Sons Ltd., 2017).\u003c/li\u003e\n\u003cli\u003eKalinowski, J., Fattori, V., Cocchi, M. \u0026amp; Williams, J. A. G. Light-emitting devices based on organometallic platinum complexes as emitters. \u003cem\u003eCoord. Chem. Rev.\u003c/em\u003e \u003cstrong\u003e255\u003c/strong\u003e, 2401-2425 (2011).\u003c/li\u003e\n\u003cli\u003eTang, M.-C., Chan, A. K.-W., Chan, M.-Y. \u0026amp; Yam, V. W.-W. Platinum and gold complexes for OLEDs. \u003cem\u003eTop. Curr. Chem.\u003c/em\u003e \u003cstrong\u003e374\u003c/strong\u003e, 46 (2016).\u003c/li\u003e\n\u003cli\u003eLiu, Y., Li, C., Ren, Z., Yan, S. \u0026amp; Bryce, M. R. All-organic thermally activated delayed fluorescence materials for organic light-emitting diodes. \u003cem\u003eNat. Rev. Mater.\u003c/em\u003e \u003cstrong\u003e3\u003c/strong\u003e, 18020 (2018).\u003c/li\u003e\n\u003cli\u003eShizu, K.\u003cem\u003e et al.\u003c/em\u003e Highly efficient electroluminescence from purely organic donor-acceptor systems. \u003cem\u003ePure Appl. Chem.\u003c/em\u003e \u003cstrong\u003e87\u003c/strong\u003e, 627-638 (2015).\u003c/li\u003e\n\u003cli\u003eCzerwieniec, R., Leitl, M. J., Homeier, H. H. H. \u0026amp; Yersin, H. Cu(I) complexes-Thermally activated delayed fluorescence. Photophysical approach and material design. \u003cem\u003eCoord. Chem. Rev.\u003c/em\u003e \u003cstrong\u003e325\u003c/strong\u003e, 2-28 (2016).\u003c/li\u003e\n\u003cli\u003eOsawa, M.\u003cem\u003e et al.\u003c/em\u003e Application of neutral d\u003csup\u003e10\u003c/sup\u003e coinage metal complexes with an anionic bidentate ligand in delayed fluorescence-type organic light-emitting diodes. \u003cem\u003eJ. Mater. Chem. C\u003c/em\u003e \u003cstrong\u003e1\u003c/strong\u003e, 4375-4383 (2013).\u003c/li\u003e\n\u003cli\u003eHatakeyama, T.\u003cem\u003e et al.\u003c/em\u003e Ultrapure blue thermally activated delayed fluorescence molecules: efficient HOMO\u0026ndash;LUMO separation by the multiple resonance effect. \u003cem\u003eAdv. Mater.\u003c/em\u003e \u003cstrong\u003e28\u003c/strong\u003e, 2777\u0026ndash;2781 (2016).\u003c/li\u003e\n\u003cli\u003eKondo, Y.\u003cem\u003e et al.\u003c/em\u003e Narrowband deep-blue organic light-emitting diode featuring an organoboron-based emitter. \u003cem\u003eNat. Photonics\u003c/em\u003e \u003cstrong\u003e13\u003c/strong\u003e, 678\u0026ndash;682 (2019).\u003c/li\u003e\n\u003cli\u003ePershin, A.\u003cem\u003e et al.\u003c/em\u003e Highly emissive excitons with reduced exchange energy in thermally activated delayed fluorescent molecules. \u003cem\u003eNat. Commun.\u003c/em\u003e \u003cstrong\u003e10\u003c/strong\u003e, 597 (2019).\u003c/li\u003e\n\u003cli\u003eNaveen, K. R., Palanisamy, P., Chae, M. Y. \u0026amp; Kwon, J. H. Multiresonant TADF materials: triggering the reverse intersystem crossing to alleviate the efficiency roll-off in OLEDs. \u003cem\u003eChem. Commun.\u003c/em\u003e \u003cstrong\u003e59\u003c/strong\u003e, 3685-3702 (2023).\u003c/li\u003e\n\u003cli\u003eSuresh, S. M., Hall, D., Beljonne, D., Olivier, Y. \u0026amp; Zysman-Colman, E. Multiresonant thermally activated delayed fluorescence emitters based on heteroatom-doped nanographenes: recent advances and prospects for organic light-emitting diodes. \u003cem\u003eAdv. Funct. Mater.\u003c/em\u003e \u003cstrong\u003e30\u003c/strong\u003e, 1908677 (2020).\u003c/li\u003e\n\u003cli\u003eHa, J. M., Hur, S. H., Pathak, A., Jeong, J.-E. \u0026amp; Woo, H. Y. Recent advances in organic luminescent materials with narrowband emission. \u003cem\u003eNPG Asia Mater.\u003c/em\u003e \u003cstrong\u003e13\u003c/strong\u003e, 53 (2021).\u003c/li\u003e\n\u003cli\u003eMonkman, A. Why do we still need a stable long lifetime deep blue OLED emitter? \u003cem\u003eACS Appl. Mater. Interfaces\u003c/em\u003e \u003cstrong\u003e14\u003c/strong\u003e, 20463\u0026ndash;20467 (2022).\u003c/li\u003e\n\u003cli\u003eKim, H. J. \u0026amp; Yasuda, T. Narrowband emissive thermally activated delayed fluorescence materials. \u003cem\u003eAdv. Optical Mater.\u003c/em\u003e \u003cstrong\u003e10\u003c/strong\u003e, 2201714 (2022).\u003c/li\u003e\n\u003cli\u003eFan, X.\u003cem\u003e et al.\u003c/em\u003e RGB thermally activated delayed fluorescence emitters for organic light-emitting diodes toward realizing the BT.2020 standard. \u003cem\u003eAdv. Sci.\u003c/em\u003e \u003cstrong\u003e10\u003c/strong\u003e, 2303504 (2023).\u003c/li\u003e\n\u003cli\u003eAziz, H. \u0026amp; Popovic, Z. D. Degradation phenomena in small-molecule organic light-emitting devices. \u003cem\u003eChem. Mater.\u003c/em\u003e \u003cstrong\u003e16\u003c/strong\u003e, 4522-4532 (2004).\u003c/li\u003e\n\u003cli\u003eSo, F. \u0026amp; Kondakov, D. Degradation mechanisms in small-molecule and polymer organic light-emitting diodes. \u003cem\u003eAdv. Mater.\u003c/em\u003e \u003cstrong\u003e22\u003c/strong\u003e, 3762-3777 (2010).\u003c/li\u003e\n\u003cli\u003eSchmidbauer, S., Hohenleutner, A. \u0026amp; K\u0026ouml;nig, B. Chemical degradation in organic light-emitting devices: mechanisms and implications for the design of new materials. \u003cem\u003eAdv. Mater.\u003c/em\u003e \u003cstrong\u003e25\u003c/strong\u003e, 2114-2129 (2013).\u003c/li\u003e\n\u003cli\u003eScholz, S., Kondakov, D., Luessem, B. \u0026amp; Leo, K. Degradation mechanisms and reactions in organic light-emitting devices. \u003cem\u003eChem. Rev.\u003c/em\u003e \u003cstrong\u003e115\u003c/strong\u003e, 8449-8503 (2015).\u003c/li\u003e\n\u003cli\u003eJeon, S. K., Lee, H. L., Yook, K. S. \u0026amp; Lee, J. Y. Recent progress of the lifetime of organic light‐emitting diodes based on thermally activated delayed fluorescent material. \u003cem\u003eAdv. Mater.\u003c/em\u003e \u003cstrong\u003e31\u003c/strong\u003e, 1803524 (2019).\u003c/li\u003e\n\u003cli\u003eKim, S.\u003cem\u003e et al.\u003c/em\u003e Degradation of blue-phosphorescent organic light-emitting devices involves exciton-induced generation of polaron pair within emitting layers. \u003cem\u003eNat. Commun.\u003c/em\u003e \u003cstrong\u003e9\u003c/strong\u003e, 1211 (2018).\u003c/li\u003e\n\u003cli\u003eMoon, Y. K.\u003cem\u003e et al.\u003c/em\u003e Modeling Electron-Transfer Degradation of Organic Light-Emitting Devices. \u003cem\u003eAdv. Mater.\u003c/em\u003e \u003cstrong\u003e33\u003c/strong\u003e, 2003832 (2021).\u003c/li\u003e\n\u003cli\u003eZhao, C., Li, C., Li, Y., Qiu, Y. \u0026amp; Duan, L. Understanding the operational lifetime expansion methods of thermally activated delayed fluorescence sensitized OLEDs: a combined study of charge trapping and exciton dynamics. \u003cem\u003eMater. Chem. Front.\u003c/em\u003e \u003cstrong\u003e3\u003c/strong\u003e, 1181-1191 (2019).\u003c/li\u003e\n\u003cli\u003eLee, Y.-T.\u003cem\u003e et al.\u003c/em\u003e Tailor-Made Multi-Resonance Terminal Emitters toward Narrowband, High-Efficiency, and Stable Hyperfluorescence Organic Light-Emitting Diodes. \u003cem\u003eAdv. Optical Mater.\u003c/em\u003e \u003cstrong\u003e10\u003c/strong\u003e, 2200682 (2022).\u003c/li\u003e\n\u003cli\u003eMeng, G.\u003cem\u003e et al.\u003c/em\u003e Highly efficient and stable deep-blue OLEDs based on narrowband emitters featuring an orthogonal spiro-configured indolo[3,2,1-\u003cem\u003ede\u003c/em\u003e]acridine structure. \u003cem\u003eChem. Sci.\u003c/em\u003e \u003cstrong\u003e13\u003c/strong\u003e, 5622-5630 (2022).\u003c/li\u003e\n\u003cli\u003eXue, W.\u003cem\u003e et al.\u003c/em\u003e Identifying the Molecular Origins of Green BN-TADF Material Degradation and Device Stability via in situ Raman Spectroscopy. \u003cem\u003eChem. Eur. J.\u003c/em\u003e \u003cstrong\u003e28\u003c/strong\u003e, e202201006 (2022).\u003c/li\u003e\n\u003cli\u003eWang, X.\u003cem\u003e et al.\u003c/em\u003e Improving the stability and color purity of a BT.2020 blue multiresonance emitter by alleviating hydrogen repulsion. \u003cem\u003eSci. Adv.\u003c/em\u003e \u003cstrong\u003e9\u003c/strong\u003e, eadh1434 (2023).\u003c/li\u003e\n\u003cli\u003eGiebink, N. C.\u003cem\u003e et al.\u003c/em\u003e Intrinsic luminance loss in phosphorescent small-molecule organic light emitting devices due to bimolecular annihilation reactions. \u003cem\u003eJ. Appl. Phys.\u003c/em\u003e \u003cstrong\u003e103\u003c/strong\u003e, 044509 (2008).\u003c/li\u003e\n\u003cli\u003eHan, S. H., Jeong, J. H., Yoo, J. W. \u0026amp; Lee, J. Y. Ideal blue thermally activated delayed fluorescence emission assisted by a thermally activated delayed fluorescence assistant dopant through a fast reverse intersystem crossing mediated cascade energy transfer process. \u003cem\u003eJ. Mater. Chem. C\u003c/em\u003e \u003cstrong\u003e7\u003c/strong\u003e, 3082-3089 (2019).\u003c/li\u003e\n\u003cli\u003eBaldo, M. A., Adachi, C. \u0026amp; Forrest, S. R. Transient analysis of organic electrophosphorescence. II. Transient analysis of triplet-triplet annihilation. \u003cem\u003ePhys. Rev. B\u003c/em\u003e \u003cstrong\u003e62\u003c/strong\u003e, 10967-10977 (2000).\u003c/li\u003e\n\u003cli\u003eGiebink, N. C., D\u0026apos;Andrade, B. W., Weaver, M. S., Brown, J. J. \u0026amp; Forrest, S. R. Direct evidence for degradation of polaron excited states in organic light emitting diodes. \u003cem\u003eJ. Appl. Phys.\u003c/em\u003e \u003cstrong\u003e105\u003c/strong\u003e, 124514 (2009).\u003c/li\u003e\n\u003cli\u003eWetzelaer, G. A. H., Kuik, M., Nicolai, H. T. \u0026amp; Blom, P. W. M. Trap-assisted and Langevin-type recombination in organic light-emitting diodes. \u003cem\u003ePhys. Rev. B\u003c/em\u003e \u003cstrong\u003e83\u003c/strong\u003e, 165204 (2011).\u003c/li\u003e\n\u003cli\u003eCreason, S. C., Wheeler, J. \u0026amp; Nelson, R. F. Electrochemical and spectroscopic studies of cation radicals. I. Coupling rates of 4-substituted triphenylaminium ion. \u003cem\u003eJ. Org. Chem.\u003c/em\u003e \u003cstrong\u003e37\u003c/strong\u003e, 4440\u0026ndash;4446 (1972).\u003c/li\u003e\n\u003cli\u003eYurchenko, O.\u003cem\u003e et al.\u003c/em\u003e Electrochemically induced reversible and irreversible coupling of triarylamines. \u003cem\u003eJ. Phys. Chem. B\u003c/em\u003e \u003cstrong\u003e116\u003c/strong\u003e, 30\u0026ndash;39 (2012).\u003c/li\u003e\n\u003cli\u003eMayer, J. M. Proton-Coupled Electron Transfer: A Reaction Chemist\u0026rsquo;s View. \u003cem\u003eAnnu. Rev. Phys. Chem.\u003c/em\u003e \u003cstrong\u003e55\u003c/strong\u003e, 363\u0026ndash;390 (2004).\u003c/li\u003e\n\u003cli\u003eKondakov, D. Y., Brown, C. T., Pawlik, T. D. \u0026amp; Jarikov, V. V. Chemical reactivity of aromatic hydrocarbons and operational degradation of organic light-emitting diodes. \u003cem\u003eJ. Appl. Phys.\u003c/em\u003e \u003cstrong\u003e107\u003c/strong\u003e, 024507 (2010).\u003c/li\u003e\n\u003cli\u003eLiu, X.\u003cem\u003e et al.\u003c/em\u003e Isotope effect of host material on device stability of thermally activated delayed fluorescence organic light-emitting diodes. \u003cem\u003eSmall Sci.\u003c/em\u003e \u003cstrong\u003e1\u003c/strong\u003e, 2000057 (2021).\u003c/li\u003e\n\u003cli\u003eTsuji, H., Mitsui, C. \u0026amp; Nakamura, E. The hydrogen/deuterium isotope effect of the host material on the lifetime of organic light-emitting diodes. \u003cem\u003eChem. Commun.\u003c/em\u003e \u003cstrong\u003e50\u003c/strong\u003e, 14870-14872 (2014).\u003c/li\u003e\n\u003cli\u003eYao, J., Dong, S.-C., Tam, B. S. T. \u0026amp; Tang, C. W. Lifetime enhancement and degradation study of blue OLEDs using deuterated materials. \u003cem\u003eACS Appl. Mater. Interfaces\u003c/em\u003e \u003cstrong\u003e15\u003c/strong\u003e, 7255\u0026ndash;7262 (2023).\u003c/li\u003e\n\u003cli\u003eAbe, T., Miyazawa, A., Konno, H. \u0026amp; Kawanishi, Y. Deuteration isotope effect on nonradiative transition of \u003cem\u003efac\u003c/em\u003e-tris (2-phenylpyridinato) iridium (III) complexes. \u003cem\u003eChem. Phys. Lett.\u003c/em\u003e \u003cstrong\u003e491\u003c/strong\u003e, 199-202 (2010).\u003c/li\u003e\n\u003cli\u003eWang, P.\u003cem\u003e et al.\u003c/em\u003e Synthesis of all-deuterated tris(2-phenylpyridine)iridium for highly stable electrophosphorescence: the \u0026ldquo;deuterium effect\u0026rdquo;. \u003cem\u003eJ. Mater. Chem. C\u003c/em\u003e \u003cstrong\u003e1\u003c/strong\u003e, 4821-4825 (2013).\u003c/li\u003e\n\u003cli\u003eBae, H. J.\u003cem\u003e et al.\u003c/em\u003e Protecting benzylic C-H bonds by deuteration doubles the operational lifetime of deep-blue Ir-phenylimidazole dopants in phosphorescent OLEDs. \u003cem\u003eAdv. Optical Mater.\u003c/em\u003e \u003cstrong\u003e9\u003c/strong\u003e, 2100630 (2021).\u003c/li\u003e\n\u003cli\u003eLi, W.\u003cem\u003e et al.\u003c/em\u003e Improved efficiency and stability of red phosphorescent organic light-emitting diodes via selective deuteration. \u003cem\u003eJ. Phys. Chem. Lett.\u003c/em\u003e \u003cstrong\u003e13\u003c/strong\u003e, 1494\u0026ndash;1499 (2022).\u003c/li\u003e\n\u003cli\u003eJung, S.\u003cem\u003e et al.\u003c/em\u003e Enhancing operational stability of OLEDs based on subatomic modified thermally activated delayed fluorescence compounds. \u003cem\u003eNat. Commun.\u003c/em\u003e \u003cstrong\u003e14\u003c/strong\u003e, 6481 (2023).\u003c/li\u003e\n\u003cli\u003eHuang, T.\u003cem\u003e et al.\u003c/em\u003e Enhancing the efficiency and stability of blue thermally activated delayed fluorescence emitters by perdeuteration. \u003cem\u003eNat. Photonics\u003c/em\u003e (2024). https://doi.org:DOI: 10.1038/s41566-024-01379-1\u003c/li\u003e\n\u003cli\u003eKaron, K. \u0026amp; Lapkowski, M. Carbazole electrochemistry: a short review. \u003cem\u003eJ. Solid State Electrochem.\u003c/em\u003e \u003cstrong\u003e19\u003c/strong\u003e, 2601\u0026ndash;2610 (2015).\u003c/li\u003e\n\u003cli\u003eParr, R. G. \u0026amp; Weitao, Y. \u003cem\u003eDensity-Functional Theory of Atoms and Molecules\u003c/em\u003e. (Oxford University Press, 1994).\u003c/li\u003e\n\u003cli\u003eNeese, F. Software Update: The ORCA Program System, Version 4.0. \u003cem\u003eWiley Interdiscip. Rev. Comput. Mol. Sci.\u003c/em\u003e \u003cstrong\u003e8\u003c/strong\u003e, e1327 (2018).\u003c/li\u003e\n\u003cli\u003eBecke, A. D. Density-Functional Exchange-Energy Approximation with Correct Asymptotic Behavior. \u003cem\u003ePhys. Rev. A Gen. Phys.\u003c/em\u003e \u003cstrong\u003e38\u003c/strong\u003e, 3098\u0026ndash;3100 (1988).\u003c/li\u003e\n\u003cli\u003eLee, C., Yang, W. \u0026amp; Parr, R. G. Development of the Colle-Salvetti Correlation-Energy Formula into a Functional of the Electron Density. \u003cem\u003ePhys. Rev. B Condens. Matter\u003c/em\u003e \u003cstrong\u003e37\u003c/strong\u003e, 785\u0026ndash;789 (1988).\u003c/li\u003e\n\u003cli\u003eGrimme, S., Antony, J., Ehrlich, S. \u0026amp; Krieg, H. A Consistent and Accurate Ab Initio Parametrization of Density Functional Dispersion Correction (DFT-D) for the 94 Elements H-Pu. \u003cem\u003eJ. Chem. Phys.\u003c/em\u003e \u003cstrong\u003e132\u003c/strong\u003e, 154104 (2010).\u003c/li\u003e\n\u003cli\u003eWeigend, F. \u0026amp; Ahlrichs, R. Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. \u003cem\u003ePhys. Chem. Chem. Phys.\u003c/em\u003e \u003cstrong\u003e7\u003c/strong\u003e, 3297-3305 (2005).\u003c/li\u003e\n\u003cli\u003eNeese, F. An Improvement of the Resolution of the Identity Approximation for the Formation of the Coulomb Matrix. \u003cem\u003eJ. Comput. Chem.\u003c/em\u003e \u003cstrong\u003e24\u003c/strong\u003e, 1740\u0026ndash;1747 (2003).\u003c/li\u003e\n\u003cli\u003eWennmohs, F., Hansen, A. \u0026amp; Becker, U. Efficient, Approximate and Parallel Hartree-Fock and Hybrid DFT Calculations. A \u0026ldquo;chain-of-Spheres\u0026rdquo; Algorithm for the Hartree-Fock Exchange. \u003cem\u003eChem. Phys.\u003c/em\u003e \u003cstrong\u003e356\u003c/strong\u003e, 98\u0026ndash;109 (2009).\u003c/li\u003e\n\u003cli\u003eWeigend, F. Accurate Coulomb-Fitting Basis Sets for H to Rn. \u003cem\u003ePhys. Chem. Chem. Phys.\u003c/em\u003e \u003cstrong\u003e8\u003c/strong\u003e, 1057\u0026ndash;1065 (2006).\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-4184912/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4184912/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003e1,4-Azaborine-based arenes gained prominence as electroluminescent emitters that exhibit thermally activated delayed fluorescence (TADF). These materials display exceptionally narrow emission spectra and high photoluminescence quantum yields, benefits arising from the multi-resonance (MR) effect. The practical application of MR-TADF emitters is often constrained by their limited operational stability. In this study, we explore the mechanism responsible for the degradation of a series of MR-TADF molecules. Electroluminescent devices employing these compounds show varied operational lifetimes, which do not align with either the excitonic stability of the emitter molecules or the degree of roll-off in external quantum efficiency. Our bulk electrolysis study reveals a considerable instability of the radical cationic forms of the MR-TADF compounds. A direct correlation is observed between device lifetime and the Faradaic yield for oxidative degradation of the emitter molecules. Comprehensive chemical analyses suggest that the degradation byproducts originate from intramolecular cyclization in the radical cation, preceded by intermolecular hydrogen atom transfer. Quantum chemical calculations indicate that this intramolecular cyclization accelerates the overall reaction, implying that cyclization reactivity is crucial for the intrinsic stability of the MR-TADF compound upon hole trapping. Our study offers an explanation for the beneficial effects of deuteration on the intrinsic stability and lays the groundwork for developing mechanism-based strategies to design MR-TADF compounds with greater operational longevity.\u003c/p\u003e","manuscriptTitle":"The Degradation Mechanism of Multi-Resonance Thermally Activated Delayed Fluorescence Materials","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-04-25 08:18:36","doi":"10.21203/rs.3.rs-4184912/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-communications","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"NCOMMS","sideBox":"Learn more about [Nature Communications](http://www.nature.com/ncomms/)","snPcode":"","submissionUrl":"https://mts-ncomms.nature.com/","title":"Nature Communications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Communications","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"79724b0c-cd14-4bd0-b9e1-bfc9f722e377","owner":[],"postedDate":"April 25th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":30749504,"name":"Physical sciences/Materials science/Materials for optics/Lasers, LEDs and light sources/Organic LEDs"},{"id":30749505,"name":"Physical sciences/Chemistry/Materials chemistry/Optical materials"}],"tags":[],"updatedAt":"2025-01-05T08:05:52+00:00","versionOfRecord":{"articleIdentity":"rs-4184912","link":"https://doi.org/10.1038/s41467-024-55620-0","journal":{"identity":"nature-communications","isVorOnly":false,"title":"Nature Communications"},"publishedOn":"2025-01-04 05:00:00","publishedOnDateReadable":"January 4th, 2025"},"versionCreatedAt":"2024-04-25 08:18:36","video":"","vorDoi":"10.1038/s41467-024-55620-0","vorDoiUrl":"https://doi.org/10.1038/s41467-024-55620-0","workflowStages":[]},"version":"v1","identity":"rs-4184912","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4184912","identity":"rs-4184912","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}