Room Temperature Proton Coupled Energy Transfer

Room Temperature Proton Coupled Energy Transfer | 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 Room Temperature Proton Coupled Energy Transfer Pi-Tai Chou, Chih-Hsing Wang, Ying-Yi Tsai, Sheng-Fu Wang, Chao-Hsien Hsu, and 9 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6244115/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted You are reading this latest preprint version Abstract Proton-coupled energy transfer (PCEnT) is new 1 and differs from traditional energy transfer in that there is virtually no ground-state tautomer population, but energy transfer can still occur by simultaneously coupling the proton transfer. PCEnT should herald a revolutionary photochemical breakthrough. However, despite theoretical advancement 2 , so far, the only PCEnT-related experiment was performed under an extreme environment (77K glass matrix) with complexity 1 . Herein, utilizing a new molecular triad AbPP comprising anthracene and bridged phenolpyridine, we provide direct and unambiguous experimental evidence for PCEnT in the room temperature solution for the first time. In cyclohexane, the rate of PCEnT for AbPP is measured to be (125 ps) -1 , which is three orders of magnitude slower than the rate of direct excited-state intramolecular proton transfer (ESIPT)((176 fs) -1 ) but yields the same 645 nm proton transfer isomer emission, supporting a weak nonadiabatic coupling process for PCEnT. This result challenges the traditional assumption that quantum processes manifest primarily at low temperatures, as it demonstrates that PCEnT—a fundamentally quantum mechanical mechanism—can occur efficiently in room-temperature solutions. Equally important, the resolved emission of proton-transfer tautomers and charge-separated states produced by PCEnT and proton-coupled electron transfer (PCET), respectively, allows for comprehensive probing of the correlation between PCEnT and PCET, with the increase of PCET rates upon increasing solvent polarity. These findings diversify the interplay among electron, proton, and energy transfer, the three fundamental mechanisms of chemical transformations. Physical sciences/Chemistry/Physical chemistry/Energy transfer Physical sciences/Chemistry/Physical chemistry/Electron transfer Figures Figure 1 Figure 2 Figure 3 Figure 4 Main Text The discovery of unconventional proton-coupled energy transfer (PCEnT) 1 based on a series of anthracene-phenol-pyridine ( APP ) triads (Scheme 1) had a significant impact on the scientific community. The concept of PCEnT is new and differs from traditional energy transfer 2-4 in that there is virtually no ground-state tautomer population to function as an energy acceptor, but energy transfer can still occur. Theoretically, PCEnT was realized by a nonadiabatic surface crossing of potential energy surfaces, where thermal fluctuations of heavy nuclei create a configuration that enables electronic energy transfer and proton tunneling to occur in a concerted fashion while preserving energy conservation. 1,5 This unique mechanism has profound implications for energy transfer-based chemical reactions, potentially reshaping our understanding of photochemical dynamics to herald a revolutionary photochemical breakthrough. However, despite theoretical advancement 5 , experimental demonstrations of PCEnT have remained limited. The only reported experiment was conducted under highly restrictive conditions, specifically in a 77 K glass matrix, where the complexity and constraints hindered definitive confirmation of PCEnT. 1 To fully validate and generalize this phenomenon, a new chemical system capable of operating under ambient conditions, such as homogeneous solutions at room temperature, is essential. Revisiting Charge-Separated State Emission Under Ambient Conditions At the beginning of this study, we revisited the reported triad 1 1,6 and found that the charge-separated state (CSS) 7 generated by excited-state proton-coupled electron transfer (PCET) 8-11 (Scheme 1B), is, in fact, emissive—contrary to earlier reports that deemed it non-emissive. We observed weak emission with a peak wavelength exceeding 600 nm, which undergoes a strong red shift as solvent polarity increases (Scheme 1C). This emission was likely overlooked in prior studies 1,6,12,13 due to insufficient sensitivity in the red and near-infrared regions. To further validate our findings, we analyzed the CSS emission lifetime data for triad 1 (Table S1 in supporting information (SI)), which matched previously reported transient absorption measurements 6,13,14 , confirming that the emission originates from the CSS. The identification of this previously unrecognized CSS emission prompted us to conduct a temperature-dependent emission study in n -butyronitrile 1,6 using 400 nm excitation, where only the anthracene moiety ( Ants, see Scheme 1A) is excited. We observed a continuous blue shift in CSS emission, from approximately 800 nm at 298 K to around 540 nm at 77 K (see Fig. S20 in SI) rather than the sudden appearance of the 540 nm emission (see ref. 1 for comparison). The continuously blue-shifted spectrum at lowering temperatures can be rationalized by an increase in solvent viscosity, hindering solvent relaxation and thus increasing the energy gap for CSS emission. These findings raise doubts about the previously assigned origin of the 540 nm emission observed in triad 1 under a 77 K glass matrix, reinforcing the need to reassess the underlying mechanisms of CSS emission under various conditions. Designing a New Triad to Enable PCEnT in Ambient Conditions The previously reported triad systems have thus far failed to provide clear experimental evidence for PCEnT, primarily because the proton transfer tautomer of their PhOH-py moiety (Scheme 1A) is non-emissive. Specifically, no LEPT (Scheme 1B) emission is observed in any solution at ambient temperature. The PhOH-py moiety has long been known to undergo ultrafast excited-state intramolecular proton transfer (ESIPT), resulting in the tautomer in the excited state that decays via an ultrafast decay process (<< 1 ps) nonradiative process. This rapid decay is attributed to the conical intersection of two potential energy surfaces (S 0 and the tautomer excited state) via torsional motion between phenyl and pyridyl rings along the C 1 -C 1 ’ bond (see Scheme 1A) 15-19 . Therefore, for triads 1–8 , both PhOH-py LEPT emission and any LEPT-related transient absorption cannot be resolved in the solution phase. Accordingly, the reported triad system also does not provide clues to probe the correlation and/or relationship between PCET and PCEnT. To address this limitation and enable the observation of both CSS and LEPT emissions, it became imperative to design new analogues of triads 1–8 . With this goal in mind, we strategically bridged the phenol and pyridine moieties of PhOH-py to develop a new triad, AbPP, composed of an anthracene derivative and a bridged phenol-pyridine fragment. The structures of AbPP and its reference compounds, namely the bridged PhOH-py ( bPP ), O - methylated PhOH-py ( OMe-bPP ), and O-methylated AbPP ( OMe-AbPP ), are depicted in Scheme 1D. The bridged bPP of AbPP limits the torsional motion of LEPT, thereby bypassing the conical intersection. Consequently, both CSS and LEPT emissions of AbPP are observable under ambient conditions. This structural modification provides an avenue to experimentally validate PCEnT and explore its relationship with PCET, resolving key uncertainties in the field. Details of this investigation are elaborated in the following sections. Probe PCEnT in nonpolar solvents The success of the designed molecules was supported by the steady-state spectroscopic measurements, which were first performed in cyclohexane because its nonpolar nature minimizes solvation perturbations. Therefore, the designed electron donor-acceptor triad A b PP , similar to the reported triads 1,6 , is expected to be PCET-free in cyclohexane to simplify the pursuit of PCEnT. First, the 320 nm excitation of reference compound b PP in cyclohexane exhibits solely a large Stokes-shifted emission maximized at ~645 nm (Fig. 1A). In comparison, OMe -bPP lacking O–H protons shows normal Stokes-shifted emission at ~360 nm in cyclohexane (Fig. S22). Unambiguously, we conclude the occurrence of ultrafast ESIPT in b PP , resulting in a 645 nm proton-transfer tautomer emission. We then probe A b PP emission by 410 nm excitation, where there is no absorption from the b PP moiety (absorption onset at ~360 nm for bPP , Fig. 1A), to ensure that only CN-Ant moiety is excited. The results (Fig. 1A) show that in addition to the CN-Ant (locally excited state, LES) emission in the 420-500 nm region, A b PP also clearly exhibits a 645 nm emission band. Upon monitoring at the 645 nm emission band, the excitation spectrum reveals the CN-Ant vibronic signature in the 360–420 nm region (Fig. S23), confirming that excitation of the CN-Ant unit indeed yields the 645 nm emission. In contrast, 410 nm excitation on OMe-A b PP that is unable to undergo proton transfer only shows blue CN-Ant emission in the 420-500 nm region (see Fig. 1B). We also performed concentration-dependent studies of A b PP and eliminated the possibility that the 645 nm emission originates from aggregation (see Fig. S25-28). These comparative studies, coupled with the spectral resemblance between the A b PP 645 nm band and b PP tautomer emission, lead us to conclude that excitation at the CN-Ant moiety of A b PP results in the b PP tautomer emission, thus providing clear spectroscopic evidence for the operation of PCEnT in A b PP . With the direct evidence of PCEnT provided, we then gained further insights into its relevant dynamics. For the reference compound bPP in cyclohexane, monitoring the proton transfer emission region of, e.g., 670 nm under 300 nm excitation (Fig. 1C) shows a fast, system-response-limited rising component (details of time-correlated single photon counting (TCSPC), see SI), accompanied by a population decay fitted to be ~36 ps. Further femtosecond fluorescence upconversion measurement gave an ultrafast rise time of tautomer of 176 fs after convoluted with the system response of 120 fs (see inset of Fig. 1C). On the other hand, in cyclohexane, upon 410 nm excitation on the CN-Ant moiety of AbPP , time-resolved data monitoring at tautomer emission clearly shows a rise and decay components fitted to be 36 ps and 136 ps, respectively (Fig. 1D). It is worth noting that the tautomer rise time of AbPP is identical to the tautomer decay of bPP (Fig. 1C), while the tautomer decay of AbPP , within the fitting uncertainty, correlates well with the decay time (125 ps) of CN-Ant (see Fig. S29). From a kinetic perspective, this result is not surprising. It indicates that the PCEnT rate of AbPP is significantly slower than the decay of the tautomer emission. Therefore, the kinetic derivation (see SI for details) clearly shows that the faster decay becomes the rising component, while the slower PCEnT becomes the decay component (Fig. 1E and 1F) of the proton-transfer tautomer emission. Accordingly, the PCEnT rate constant for AbPP in cyclohexane was concluded to be (125 ps) -1 , yielding a proton-transfer tautomer emission with a decay lifetime of 36 ps. Using AbPP we therefore provide direct and unequivocal experimental evidence for PCEnT. Considering yielding the same proton transfer tautomer, the k PCEnT = (125 ps) -1 of AbPP in cyclohexane is three orders of magnitude slower than that of direct ultrafast ESIPT of bPP ((176 fs) -1 ), supporting that PCEnT is associated with a weak nonadiabatic coupling process 5 . Observing emissions from PCEnT and PCET processes in polar solvents Equally important as the evidence for PCEnT is to probe the relationship between PCEnT and PCET in polar solvents where PCET is expected to occur 1,6,12 . Fig. 2 shows the absorption and emission spectra of A b PP in various solvents. Two excitation regions, 320 nm and 410 nm are applied here. The 320 nm excitation is primarily targeted at the b PP moiety of A b PP , which mainly undergoes direct, ultrafast ESIPT at a rate (~176 fs, see Fig. 1C) that exceeds all other excited-state relaxation pathways, leading to 645 nm tautomer emission band, the spectral feature of which is nearly independent of solvent polarity (see Fig. 2A, blue curves ). On the other hand, with 410 nm excitation that is exclusively on the CN-Ant moiety of AbPP , an emission band in the 600–700 nm range was observed (Fig. 2A, black curves). A normalized zoom-in comparison with the emission excited at 320 nm revealed that the emission band under 410 nm excitation exhibited a red shift with increasing solvent polarity (Fig. 2B). Given that the proton-transfer tautomer spectral characteristics of direct ESIPT are nearly independent of solvent polarity (see Fig. 1A), this red-shifted emission band suggests the appearance of an additional longer-wavelength emission band in addition to the 645 nm tautomer emission. Although two bands cannot be distinctly separated due to the significant spectral overlap, the new band seems to increase in intensity and red-shifted with a trend of increasing polarity from dichloromethane (DCM), D7A1 (7:1 v/v DCM /acetonitrile (ACN)), to D6A1 (6:1 v/v DCM /ACN)) (Fig. 2B). In highly polar solvents such as ACN, both emissions decrease significantly and become obscure. Based on the CSS emission resolved from triad 1 in this study (Scheme 1C) and the fact that A b PP is a homolog of triads 1-8 (Scheme 1A), it is reasonable to assign the new band of A b PP in polar solvents to the CSS emission generated by PCET. Relative to CSS, for convenience of discussion, the excited proton transfer tautomer of A b PP is denoted as LEPT to be consistent with the previous assignment 1,6,12 . Despite the spectral overlap between CSS and LEPT emissions in A b PP , their unique electronic characteristics enabled differentiation. The CSS emission exhibits solvatochromism due to its spatial charge separation, as shown in Scheme 1C for triad 1 and Fig. 2 for A bPP . On the other hand, LEPT has elongated p-conjugation and minimal net charge transfer, for which the emission is essentially unaffected by the solvent polarity, as supported by the 645 nm peak wavelength in all studied solvents (Fig. 2). These findings confirm that the 410 nm excitation at the CN-Ant moiety of A bPP activates both PCEnT and PCET in room temperature polar solutions, giving LEPT and CSS emissions. However, despite the appropriate assignment, steady-state emission data alone do not illustrate the relationship between these two pathways. For example, are PCEnT and PCET in polar solvents following a sequential path? If so, what is the order of reaction? Or are they in parallel competing processes? Resolving this ambiguity requires gaining insights into their relaxation dynamics. Also, Fig. 2C presents the steady-state emission contributions of LEPT and CSS, with their deconvolution performed through kinetic analysis in the following section. Kinetic expression of PCEnT and PCET Resolvable emission in each state allows us to apply femtosecond fluorescence upconversion and TCSPC methods to probe emission early relaxation dynamics and population decay, respectively. In this study, unless otherwise specified, the excitation wavelength was mainly fixed at 410 nm to excite the CN-An t chromophore. The LES emission of A b PP was monitored at 440 nm (the typical CN-Ant emission), while CSS and LEPT emissions were monitored at > 600 nm to avoid any interference by the LES emission. The representative relaxation dynamics and relevant kinetic data of A b PP in DCM and D7A1 are depicted in Fig. 3. It is worth noting that the emission in ACN is shifted toward near-infrared and is of small intensity; therefore, the fluorescence upconversion data introduce large uncertainty. Alternatively, femtosecond transient absorption (TA) measurements were applied to probe the dynamics of CSS/LEPT in ACN (Fig. S34, see SI for detail). As shown in Fig. 3A, the LES 440 nm emission of A b PP in DCM reveals a fast decay with a lifetime of 7.5 ps, which correlates well with 7.3 ps of the rise component monitored at emission at e.g., 700 nm. Extending the acquisition time through TCSPC method, the emission decay curve at >600 nm clearly consists of two components (Fig. 3B) with decay lifetime fitted to be 40 ps and 443 ps (Table 1). The intensity ratio of these two components depends on the emission wavelength, as demonstrated by the emission monitored at 600, 650, and 700 nm (see Fig. 3B and 3C). The results clearly support the emission at > 600 nm consisting of two excited-state species, most plausibly LEPT and CSS. In DCM, the lifetime of proton-transfer tautomer emission of reference compound b PP is determined to be 38 ps (see Table S3). Therefore, for A b PP , it is reasonable to attribute the 40 ps decay component in DCM to the LEPT emission. Accordingly, the 443 ps component originates from the CSS emission. Furthermore, at the emission of > 600 nm, independent of the monitored wavelength, the rise component in DCM is fitted to be within 7.3 ps, which is equal to the decay time of the LES emission. The results indicate that both LEPT and CSS are populated from the same origin, i.e., the LES, but undergo different population decays. Briefly, under 410 nm excitation of A b PP in DCM, the LES undergoes parallel PCEnT and PCET pathways at a total rate of (7.5 ps) -1 , leading to LEPT and CSS emissions with a lifetime of 40 and 443 ps, respectively. Similar relaxation kinetics for AbPP were observed in other polar solvents, i.e., the rise time of LEPT and CSS was the same as the decay time of LES, while the decay times of LEPT and CSS were significantly different (Table 1). Furthermore, the intensity ratio of LEPT to CSS emissions showed emission wavelength dependence; the evidence is given by AbPP in DCM (Fig. 3B and 3C) and in D7A1 (Fig. 3E and 3F). Importantly, the sum of PCEnT and PCET rates increase with increasing the solvent polarity, which is in the order of (31.8 ps) -1 in toluene < (7.5 ps) -1 in DCM < (5.8 ps) -1 in D7A1 < (2.8 ps) -1 in ACN. The next issue that needs to be addressed is the branching ratio of PCEnT to PCET. Although the rates of PCEnT/PCET cannot be separated without knowing the individual product CSS and LEPT distribution, the PCET rate involving charge transfer must be strongly dependent on the solvent polarity, whereas PCEnT, as supported by the same emission peak wavelength and lifetime in various solvents, is expected to be solvent independent. Therefore, it is reasonable to assume that the PCEnT rate in the solvents studied is similar, i.e., equivalent to the PCEnT rate of (125 ps) -1 in cyclohexane. Consequently, the rates of PCET in toluene, DCM, D7A1, and ACN are deduced to be (42.6 ps) -1 , (8.0 ps) -1 , (6.1 ps) -1 and (2.9 ps) -1 , respectively, showing the trend of increasing PCET rate upon the increase of the solvent polarity. In other words, the PCET of A b PP is in the Marcus normal region 1,6,12 . We then combined steady-state and kinetic results to deduce the contributions of CSS and LEPT in the steady-state emission spectra. In this approach, the emission ratios were analyzed by integrating kinetic decay curves to determine the intensity contribution at different monitoring wavelengths, where the decay curves were used to calculate the intensity ratio of CSS to LEPT emissions (see Fig. 3C and 3F in DCM and D7A1, respectively). The resulting data were then used as initial guesses for spectral fitting of the steady-state emission band between 600-800 nm in various solvents. Fig. 2C illustrates the evolution of the contribution ratio of CSS to LEPT emissions for AbPP in the studied solvents. The results clearly indicate that the LEPT state is minimally affected by solvent polarity, yielding a constant emission peak position at ~645 nm (blue shaded portion of Fig. 2C). In stark contrast, the CSS state, characterized by significant charge separation, exhibits a clear solvatochromism phenomenon (shaded red) with a peak wavelength red-shifted from 650 nm (in toluene) to the near-infrared region (in ACN, see inset of Fig. 2C). In ACN, the fast PCET (2.86 ps) -1 leads to a small branching ratio of LEPT production. This, together with the NIR CSS emission that is subject to dominant radiationless quenching, gives obscure LEPT and CSS emissions in ACN. Table 1 The fitted rise and decay time constants of various emission components in AbPP under 410 nm excitation in various solvents. a. D7A1 is mixture of DCM:ACN = 7:1 (v:v) b . Lifetimes measured using the TCSPC technique. c. Lifetimes are measured using the upconversion technique. d. Lifetimes measured using TA. For more details, refer to the supporting information. An important question that remains concerns the electron transfer between LEPT and CCS, which seems to be prohibited in AbPP due to two separate and distinct population decay times. If they were interconverted during the excited state lifetime, the same population decay would have been observed. We suspect that the failure of interconversion in AbPP is due to the rapid decay of LEPT emission (35-40 ps), which is governed by the deactivation of the partially flexible C 1 -C 1 ’ torsional motion (Scheme 1A). On the other hand, LEPT → CCS charge transfer or vice versa (see Fig. 4) is expected to be much slower due to the larger spatial distance between donor and acceptor. From another perspective, the rates of PCEnT and PCET are faster than LEPT ↔ CCS electron transfer in AbPP because both PCEnT and PCET simultaneously involve proton transfer that acts as a driving force to accelerate the reaction. Interestingly, if the LEPT emission lifetime is long enough, say a few nanoseconds, then interconversion between LEPT and CSS is expected to occur. This remains to be resolved by new triads in the future. Conclusion By restricting, in part, the C 1 -C 1 ’ torsional motion of PhOH-py moiety in a newly designed triad, AbPP , we reveal the spectroscopic signatures for both LEPT and CSS emissions in solution at room temperature. In nonpolar solvents such as cyclohexane, the excitation at the anthracene moiety ( CN-Ant ) gives rise to the bPP tautomer emission with a rate constant of (125 ps) -1 , providing direct evidence for PCEnT. The rate of PCEnT is three orders of magnitude slower than direct ESIPT in bPP, which proceeds at ~ (176 fs) -1 , highlighting the role of weak nonadiabatic coupling in facilitating PCEnT, in line with theoretical predictions. 5 . As shown in Fig. 4 , PCEnT and PCET are concurrently two competitive reaction pathways, where the branching ratio for the rate of PCEnT to PCET decreases as increasing the solvent polarity. The CSS emission peak is strongly dependent on solvent polarity, shifting from 650 nm in toluene to approximately 1000 nm in ACN, accompanied by an increase in nonradiative quenching processes. These results establish a solid experimental framework for understanding PCEnT in ambient conditions and its interplay with PCET, providing a connection between these fundamental processes. Beyond its mechanistic significance, our findings challenge the prevailing view that quantum processes are largely restricted to low temperatures. We show that PCEnT, which is an intrinsically quantum mechanical phenomenon, operates efficiently in room-temperature solutions, expanding the conceptual framework of energy transfer. The integration of electron, proton, and energy transfer in a single system has broad implications across biological, chemical, and optoelectronic contexts, paving the way for further exploration of quantum-driven reaction pathways under ambient conditions. Method Synthesis. All reactions were performed under a nitrogen atmosphere unless otherwise noted. Solvents were distilled from appropriate drying agents prior to use. Commercially available reagents were used without further purification. Mass spectra were obtained on JEOL AccuTOF GCX instrument operating in field desorption (FD). 1 H NMR (400 MHz) and 13 C NMR (100 MHz) spectra were recorded on Bruker AVIII HD 400MHz NMR and Agilent Unity + 400MHz NMR. X-ray diffraction was conducted on Bruker AXS D8 VENTURE, PhotonIII_C28. Photophysical Measurements. All photophysical measurements in this study, unless otherwise specified, were performed at room temperature (298 K). UV‒visible absorption spectra were recorded on a UV‒visible NIR spectrophotometer system (HITACHI UH5700). The steady-state emission spectra and excitation spectra were measured with a spectrofluorometer (Edinburgh FL 980). Both the wavelength-dependent excitation and emission responses were calibrated. The emission QY in solution was calculated using 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCMP) as a reference dye, for which the photoluminescence quantum yield (PLQY) is 44% in methanol 20 . All measurements were conducted using a 10-mm square cell unless otherwise noted. Steady-state temperature-dependent fluorescence was also measured with a spectrofluorometer (Edinburgh FL 980). The temperature was set by a cryostat (Specac, P/N GS21525 DN1704) with a controller. An equilibration time of at least thirty minutes was supplied between temperatures, cooling the sample using N 2 (l), while maintaining a high vacuum within the chamber. The samples were contained within quartz (CFQ) EPR tubes – 5mm outer diameter, with concentration ~ 1.0 × 10 − 5 M. The picosecond time-resolved studies were performed by a time-correlated single photon counting (TCSPC) technique where a ~ 120 fs laser (410 and 300 nm) was used as a pumping source, which incorporated with a microchannel detector gives a time resolution of ~ 15 ps. As for the fluorescence upconversion measurement, a stable 120-fs LASER oscillator performed this ultrafast fluorescence upconversion measurement (FOG100-DX, CDP corp.). A PUMP beam of 410 and 300 nm was generated by the part of the oscillator output traveling through the second and third harmonic generation (SHG and THG, β-barium borate crystal). An iris selected the energy and the beam size of PUMP after this SHG and THG. The lens system was used to focus PUMP on the sample, to collect the fluorescence, and to focus the fluorescence on sum-frequency BBO crystal (SHG and THG, β-barium borate crystal), respectively. The entitled compounds are measured in a rotated cell with a transmitted collection mode. The GATE beam (820 and 900 nm) enters the delay line stage and crosses the fluorescence beam in the sum-frequency BBO with a collinear measurement. The polarized angle between PUMP and GATE is set at the magic angle (54.7˚). A monochromator was applied and coupled with a PMT to record the sum-frequency signal. In this research, the FWHM of IRF is ~ 150 fs. Femtosecond transient absorption (fs-TA) setup of our light source is schematically illustrated in the previous work. 21 Briefly speaking, the measurements were performed using a commercial Yb: KGW laser system (Pharos, Light Conversion) with a central wavelength of 1030 nm, an average power of 2.5 W, a repetition rate of 3.125 kHz, a pulse energy of 800 µJ and a pulse duration of 190 fs. Two identical pulses were produced with a low-GDD 50/50 beam splitter and passed through our designed nonlinear compressor, named multiple plate compression (MPC). For this experiment, a high-pass filter with a cut-off wavelength of 980 nm was applied. Pulse compression was achieved with 8 chirped mirror bounces (Ultrafast Innovation), thus removing the material dispersion introduced by the optics before the sample. The compressed pulses had an FWHM duration of 3.2 fs and were characterized at the sample position with a polarization-gating frequency-resolved optical gating (PG-FROG). Declarations Acknowledgments We acknowledge the Instrument Centre, National Taiwan University of Taiwan for the use of the facilities. We thank Mr. Y.-H. Liu of Instrument Centre, National Taiwan University for the assistance in X-ray measurements. Funding This work was supported by the National Science and Technology Council, R.O.C. Academia Sinica, Taiwan, AS-CDA-111-M02 to L.-Y.H. National Science and Technology Council, Taiwan, 111-2113-M-001-027-MY4 to L.-Y.H. Physics Division of the National Center for Theoretical Sciences, Taiwan, 112-2124-M-002-003 to L.-Y.H. National Science and Technology Council, Taiwan, 112-2113-M-002-011-MY3 to C.-T.C. National Science and Technology Council, Taiwan, 113-2639-M-002-001-ASP to P.-T.C. This research was also supported by the UMC Fellowship. Author contributions P. -T. C. conceived the research and designed the experiments. S. -F. W., C. -Y. L., Y. -C. C., and Y. -S. T. Y. executed the synthesis and characterization of all studied compounds and grew the corresponding crystals. C. -P. H. conducted the cyclic voltammetry (CV) measurement of designed samples. Y. -Y. T., C. -H. W., H. -T. Q., and C. -H. H. conducted optical measurements and analyzed the data. Y. -C. W., Y. -C. C., L. -Y. H., C. -T. C., and P. -T. C. supervised the project. C. -H. W., Y. -Y. T., and P. -T. C. wrote the manuscript. Competing interests The authors declare no competing interests. Data and materials availability All data are available in the main text or the supplementary materials. References Pettersson Rimgard, B. et al. Proton-coupled energy transfer in molecular triads. Science 377 , 742-747 (2022). Förster, T. Zwischenmolekulare Energiewanderung und Fluoreszenz. Ann. Phys. 437 , 55-75 (1948). Silbey, R. Electronic energy transfer in molecular crystals. Annu. Rev. Phys. Chem. 27 , 203-223 (1976). Scholes, G. D. Long-range resonance energy transfer in molecular systems. 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Siteselective and Enantiocomplementary C(sp3)–H Oxyfunctionalization for Synthesis of α-Hydroxy Acids. ACS Catal. 14 , 4463-4470 (2024). Castillo-Rangel, N., Pérez-Díaz, J. O. H. & Vázquez, A. An Expeditious Synthesis of 8-Methoxy-1-tetralone. Synth. 48 , 2050-2056 (2016). Okamoto, K., Watanabe, M., Murai, M., Hatano, R. & Ohe, K. Practical synthesis of aromatic nitrilesviagallium-catalysed electrophilic cyanation of aromatic C–H bonds. Chem. Commun. 48 , 3127-3129 (2012). Scheme Scheme 1 is available in the Supplementary Files section. Additional Declarations There is NO Competing Interest. Supplementary Files NatureSupplementaryMaterial2025317.pdf Supplementary Information d25304CCDC2421278OMeAbPP.cif d25304_CCDC 2421278_OMe-Abpp.cif Scheme1.docx ic22917CCDC2421279AbPP.cif ic22917_CCDC 2421279_AbPP.cif Cite Share Download PDF Status: Under Review 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. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. 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-6244115","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":462691486,"identity":"ccc911af-a6ab-49f0-8d27-ea487e8489c5","order_by":0,"name":"Pi-Tai Chou","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAApUlEQVRIiWNgGAWjYDACCSD+AGEaEK+FcQZENZBIIFILMw9JWvhnNx97bLvjT2IDe/M2CcYfh4mw5M6xdOPcMwaJDTzHyiQYEojQYiCRYyad2wbUAmQAtdwmUoslSIv8G1K0MIJt4SFSi8SNtHTD3jZj4zaetGKLhLT/hLXwz0g+9uBnm5xsP/vhjTc+2KQR1gIEbAgygSgNMC2jYBSMglEwCnACAF7wMlZpDY+pAAAAAElFTkSuQmCC","orcid":"https://orcid.org/0000-0002-8925-7747","institution":"National Taiwan University","correspondingAuthor":true,"prefix":"","firstName":"Pi-Tai","middleName":"","lastName":"Chou","suffix":""},{"id":462691487,"identity":"19919a7d-871e-43ee-b92c-ba3e4020391e","order_by":1,"name":"Chih-Hsing Wang","email":"","orcid":"","institution":"National Taiwan University","correspondingAuthor":false,"prefix":"","firstName":"Chih-Hsing","middleName":"","lastName":"Wang","suffix":""},{"id":462691488,"identity":"2a619e0e-c491-473a-83ab-488fef9ce4c0","order_by":2,"name":"Ying-Yi 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University","correspondingAuthor":false,"prefix":"","firstName":"Chien-Yu","middleName":"","lastName":"Lai","suffix":""},{"id":462691492,"identity":"8d9850be-461b-41b0-8de1-83ae6473a249","order_by":6,"name":"Yu‐Chen Wei","email":"","orcid":"","institution":"Department of Chemistry, National Taiwan University","correspondingAuthor":false,"prefix":"","firstName":"Yu‐Chen","middleName":"","lastName":"Wei","suffix":""},{"id":462691493,"identity":"de215cc4-8617-4ece-9014-7f51de901bc0","order_by":7,"name":"Chih-Pin Han","email":"","orcid":"","institution":"Department of Chemistry, National Taiwan University","correspondingAuthor":false,"prefix":"","firstName":"Chih-Pin","middleName":"","lastName":"Han","suffix":""},{"id":462691494,"identity":"cad3cacc-d214-402d-82de-5dd7ef753302","order_by":8,"name":"Hao-Ting Qu","email":"","orcid":"","institution":"Department of Chemistry, National Taiwan 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University","correspondingAuthor":false,"prefix":"","firstName":"Yuan-Chung","middleName":"","lastName":"Cheng","suffix":""},{"id":462691498,"identity":"3816d80c-c2c7-47e3-a833-e147e8280aef","order_by":12,"name":"Liang-Yan Hsu","email":"","orcid":"https://orcid.org/0000-0001-9165-1033","institution":"Institute of Atomic and Molecular Sciences, Academia Sinica","correspondingAuthor":false,"prefix":"","firstName":"Liang-Yan","middleName":"","lastName":"Hsu","suffix":""},{"id":462691499,"identity":"ea998af6-006c-42b9-a84c-778a376b258c","order_by":13,"name":"Chao-Tsen Chen","email":"","orcid":"https://orcid.org/0000-0002-7225-4873","institution":"National Taiwan University","correspondingAuthor":false,"prefix":"","firstName":"Chao-Tsen","middleName":"","lastName":"Chen","suffix":""}],"badges":[],"createdAt":"2025-03-17 11:30:09","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6244115/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6244115/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":83591383,"identity":"a50a5287-e5cf-4c24-83ce-ddf131e075c0","added_by":"auto","created_at":"2025-05-29 06:21:41","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":1225118,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eSteady-state spectra and emission kinetics in solutions\u003c/strong\u003e (\u003cstrong\u003eA\u003c/strong\u003e) Absorption and emission spectra of \u003cstrong\u003eAbPP\u003c/strong\u003e in cyclohexane and \u003cstrong\u003ebPP\u003c/strong\u003e in cyclohexane or DCM. The \u003cstrong\u003ebPP\u003c/strong\u003e and \u003cstrong\u003eAbPP\u003c/strong\u003e spectra (excited at 320 nm) both feature a 645 nm emission band, attributed to the tautomer LEPT state. (\u003cstrong\u003eB\u003c/strong\u003e) Absorption and emission spectra of \u003cstrong\u003eOMe-AbPP\u003c/strong\u003e in cyclohexane. The emission is acquired by excitation at 320 and 410 nm, showing only anthracene emission. (\u003cstrong\u003eC\u003c/strong\u003e) TCSPC relaxation dynamics of \u003cstrong\u003ebPP\u003c/strong\u003e in cyclohexane (excited at 300 nm) monitored at 670 nm, with a 36 ps decay. Inset: ultrafast rise (~176 fs) acquired via fluorescence upconversion. (\u003cstrong\u003eD\u003c/strong\u003e) \u003cstrong\u003eAbPP\u003c/strong\u003e excitation at 410 nm in cyclohexane, showing 36 ps and 125 ps rise and decay times at 670 nm. (\u003cstrong\u003eE\u003c/strong\u003e) Schematic of ESIPT in \u003cstrong\u003ebPP\u003c/strong\u003e and PCEnT pathways in \u003cstrong\u003eAbPP\u003c/strong\u003e, illustrating the kinetic relationship of the proposed PCEnT mechanism in a nonpolar solvent. (\u003cstrong\u003eF\u003c/strong\u003e) A mathematical explanation of why the faster decay appears as the rising component, while the slower PCEnT process corresponds to the decay component of the proton-transfer tautomer emission. The 𝑘\u003csub\u003ePCEnT\u003c/sub\u003e is the rate constant of PCEnT from LES to LEPT, and 𝑘\u003csub\u003eLES\u003c/sub\u003e and 𝑘\u003csub\u003eLEPT\u003c/sub\u003e are the rate constant for LES and LEPT population decay, respectively. The negative and positive pre-exponential values indicate the rise and decay components, respectively. In (\u003cstrong\u003eC\u003c/strong\u003e) and (\u003cstrong\u003eD\u003c/strong\u003e), the grey shaded peak represents the instrument response function (IRF), black curves are fitting lines and scatter points are experimental data.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-6244115/v1/a92a33c748da04eb7b0f332e.png"},{"id":83591856,"identity":"fa223a66-8125-45ef-b1eb-93aefc78c9c6","added_by":"auto","created_at":"2025-05-29 06:29:41","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":997924,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eAbsorption and emission spectra of AbPP in various solvents.\u003c/strong\u003e (\u003cstrong\u003eA\u003c/strong\u003e) From left to right, the absorption and emission spectra of \u003cstrong\u003eAbPP\u003c/strong\u003e are shown for solvents ranging from nonpolar to polar environment: cyclohexane, toluene, DCM, D7A1, D6A1 (mixed solvents with 7:1 and 6:1 volume ratios of DCM to ACN), and ACN. Excitation at 320 nm and 410 nm highlights the effects of selectively pumping \u003cstrong\u003ebPP\u003c/strong\u003e and \u003cstrong\u003eCN-Ant\u003c/strong\u003e moieties, respectively. The low-energy emission band around 600–700 nm is observed under both excitation wavelengths. (\u003cstrong\u003eB\u003c/strong\u003e) provides a magnified view of the normalized emission bands in the 600-800 nm region under 320 and 410 nm excitation for different polarities of solvents.\u003cstrong\u003e (C) \u003c/strong\u003eThe deconvolution of the steady-state low-energy broadband emission, with LEPT contributions shown in blue and CSS contributions in red, highlighting their variation across solvents of different polarities (see kinetic expression section for detail). The CSS emission peak exhibits a noticeable red shift with increasing solvent polarity, whereas LEPT remains unaffected by polarity changes. Inset of the far right panel: The emission in the near-infrared (NIR) region for \u003cstrong\u003eAbPP\u003c/strong\u003e in ACN confirms the significant solvatochromism of \u003cstrong\u003eAbPP\u003c/strong\u003ein ACN.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-6244115/v1/f3323b0446bbb3448d5e37dc.png"},{"id":83591210,"identity":"9e9bcf47-d935-4ae4-abed-0a68478165a0","added_by":"auto","created_at":"2025-05-29 06:13:41","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":711883,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eAnalysis of emission contributions from CSS and LEPT.\u003c/strong\u003e The relaxation dynamics of \u003cstrong\u003eAbPP\u003c/strong\u003e in DCM (\u003cstrong\u003eA\u003c/strong\u003e, \u003cstrong\u003eB, C\u003c/strong\u003e) and D7A1 (\u003cstrong\u003eD\u003c/strong\u003e, \u003cstrong\u003eE, F\u003c/strong\u003e). All measurements were performed under 410 nm excitation. \u003cstrong\u003eA\u003c/strong\u003e and \u003cstrong\u003eD\u003c/strong\u003e panels are acquired by fluorescence upconversion, while \u003cstrong\u003eB\u003c/strong\u003e and \u003cstrong\u003eE\u003c/strong\u003e panels are obtained from TCSPC measurement. \u003cstrong\u003eC \u003c/strong\u003eand \u003cstrong\u003eF\u003c/strong\u003e: The percentage of LEPT and CSS contribution in intensity monitored at different emission wavelengths for \u003cstrong\u003eAbPP \u003c/strong\u003ein DCM (\u003cstrong\u003eC\u003c/strong\u003e) and D7A1 (\u003cstrong\u003eF\u003c/strong\u003e).\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-6244115/v1/0b6770724ded052743c58aea.png"},{"id":83591214,"identity":"41f7e82f-84a7-481f-8373-0f9ac98ca157","added_by":"auto","created_at":"2025-05-29 06:13:41","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":353467,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ePotential energy surfaces associated with PCEnT and PCET in AbPP triad.\u003c/strong\u003e This schematic illustrates the proposed mechanism based on the steady-state and time-resolved spectroscopy. Transitions from LES to CSS and LES to LEPT are identified as two competitive pathways, representing the parallel processes of PCET and PCEnT. The findings suggest that CSS and LEPT are coupled with LES via distinct vibrational modes in separate domains. Both transitions involve proton transfer: CSS proceeds through PCET, while LEPT occurs via PCEnT.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-6244115/v1/dda47438f7125b4798013e91.png"},{"id":85327674,"identity":"bd0916b6-b742-4c4e-b626-c999daad0be6","added_by":"auto","created_at":"2025-06-24 16:59:36","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4500358,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6244115/v1/69fa768f-bc73-40f1-91b0-754b24ac6712.pdf"},{"id":83591392,"identity":"75e0ad39-b205-41f9-85ce-f581c098853a","added_by":"auto","created_at":"2025-05-29 06:21:41","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":3766832,"visible":true,"origin":"","legend":"Supplementary Information","description":"","filename":"NatureSupplementaryMaterial2025317.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6244115/v1/bf478663c76e61984c71709f.pdf"},{"id":83591232,"identity":"2eb1e915-4741-41fd-a913-31d76a0d120d","added_by":"auto","created_at":"2025-05-29 06:13:41","extension":"cif","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":757481,"visible":true,"origin":"","legend":"d25304_CCDC 2421278_OMe-Abpp.cif","description":"","filename":"d25304CCDC2421278OMeAbPP.cif","url":"https://assets-eu.researchsquare.com/files/rs-6244115/v1/89236a9558ea26f29d9b456b.cif"},{"id":83591385,"identity":"c9c93336-8ccd-463e-90c6-70a2f90130b2","added_by":"auto","created_at":"2025-05-29 06:21:41","extension":"docx","order_by":3,"title":"","display":"","copyAsset":false,"role":"supplement","size":304984,"visible":true,"origin":"","legend":"","description":"","filename":"Scheme1.docx","url":"https://assets-eu.researchsquare.com/files/rs-6244115/v1/93666ffea545562301b0a286.docx"},{"id":83591861,"identity":"6984e322-baa6-4123-9c0e-7c27c173743b","added_by":"auto","created_at":"2025-05-29 06:29:41","extension":"cif","order_by":4,"title":"","display":"","copyAsset":false,"role":"supplement","size":874426,"visible":true,"origin":"","legend":"ic22917_CCDC 2421279_AbPP.cif","description":"","filename":"ic22917CCDC2421279AbPP.cif","url":"https://assets-eu.researchsquare.com/files/rs-6244115/v1/ed6cb12311122eb7c7ce5eb2.cif"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Room Temperature Proton Coupled Energy Transfer","fulltext":[{"header":"Main Text","content":"\u003cp\u003eThe discovery of unconventional proton-coupled energy transfer (PCEnT)\u003csup\u003e1\u003c/sup\u003e based on a series of anthracene-phenol-pyridine (\u003cstrong\u003eAPP\u003c/strong\u003e) triads (Scheme 1)\u0026nbsp;had a significant impact on the scientific community. The concept of PCEnT is new and differs from traditional energy transfer\u003csup\u003e2-4\u003c/sup\u003e in that there is virtually no ground-state tautomer population to function as an energy acceptor, but energy transfer can still occur. Theoretically, PCEnT was realized by a nonadiabatic surface crossing of potential energy surfaces, where thermal fluctuations of heavy nuclei create a configuration that enables electronic energy transfer and proton tunneling to occur in a concerted fashion while preserving energy conservation.\u003csup\u003e1,5\u003c/sup\u003e This unique mechanism has profound implications for energy transfer-based chemical reactions, potentially reshaping our understanding of photochemical dynamics to herald a revolutionary photochemical breakthrough. However, despite theoretical advancement\u003csup\u003e5\u003c/sup\u003e, experimental demonstrations of PCEnT have remained limited. The only reported experiment was conducted under highly restrictive conditions, specifically in a 77 K glass matrix, where the complexity and constraints hindered definitive confirmation of PCEnT.\u003csup\u003e1\u003c/sup\u003e To fully validate and generalize this phenomenon, a new chemical system capable of operating under ambient conditions, such as homogeneous solutions at room temperature, is essential.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eRevisiting Charge-Separated State Emission Under Ambient Conditions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAt the beginning of this study, we revisited the reported \u003cstrong\u003etriad 1\u003c/strong\u003e\u003csup\u003e1,6\u003c/sup\u003e and found that the charge-separated state (CSS)\u003csup\u003e7\u003c/sup\u003e generated by excited-state proton-coupled electron transfer (PCET)\u003csup\u003e8-11\u003c/sup\u003e (Scheme 1B), is, in fact, emissive\u0026mdash;contrary to earlier reports that deemed it non-emissive. We observed weak emission with a peak wavelength exceeding 600 nm, which undergoes a strong red shift as solvent polarity increases (Scheme 1C). This emission was likely overlooked in prior studies\u003csup\u003e1,6,12,13\u003c/sup\u003e due to insufficient sensitivity in the red and near-infrared regions. To further validate our findings, we analyzed the CSS emission lifetime data for \u003cstrong\u003etriad 1\u003c/strong\u003e (Table S1 in supporting information (SI)), which matched previously reported transient absorption measurements\u003csup\u003e6,13,14\u003c/sup\u003e, confirming that the emission originates from the CSS. The identification of this previously unrecognized CSS emission prompted us to conduct a temperature-dependent emission study in \u003cem\u003en\u003c/em\u003e-butyronitrile\u003csup\u003e1,6\u003c/sup\u003e using 400 nm excitation, where only the anthracene moiety (\u003cstrong\u003eAnts,\u0026nbsp;\u003c/strong\u003esee Scheme 1A) is excited. We observed a continuous blue shift in CSS emission, from approximately 800 nm at 298 K to around 540 nm at 77 K (see Fig. S20 in SI) rather than the sudden appearance of the 540 nm emission (see ref. \u003csup\u003e1\u003c/sup\u003e for comparison). The continuously blue-shifted spectrum at lowering temperatures can be rationalized by an increase in solvent viscosity, hindering solvent relaxation and thus increasing the energy gap for CSS emission. These findings raise doubts about the previously assigned origin of the 540 nm emission observed in \u003cstrong\u003etriad 1\u003c/strong\u003e under a 77 K glass matrix, reinforcing the need to reassess the underlying mechanisms of CSS emission under various conditions.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDesigning a New Triad to Enable PCEnT in Ambient Conditions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe previously reported triad systems have thus far failed to provide clear experimental evidence for PCEnT, primarily because the proton transfer tautomer of their\u003cstrong\u003e\u0026nbsp;PhOH-py\u003c/strong\u003e moiety (Scheme 1A) is non-emissive. Specifically, no LEPT (Scheme 1B) emission is observed in any solution at ambient temperature. The \u003cstrong\u003ePhOH-py\u003c/strong\u003e moiety has long been known to undergo ultrafast excited-state intramolecular proton transfer (ESIPT), resulting in the tautomer in the excited state that decays via an ultrafast decay process (\u0026lt;\u0026lt; 1 ps) nonradiative process. This rapid decay is attributed to the conical intersection of two potential energy surfaces (S\u003csub\u003e0\u003c/sub\u003e and the tautomer excited state) via torsional motion between phenyl and pyridyl rings along the C\u003csub\u003e1\u003c/sub\u003e-C\u003csub\u003e1\u003c/sub\u003e\u0026rsquo; bond (see Scheme 1A) \u003csup\u003e15-19\u003c/sup\u003e. Therefore, for\u003cstrong\u003e\u0026nbsp;triads 1\u0026ndash;8\u003c/strong\u003e, both \u003cstrong\u003ePhOH-py\u003c/strong\u003e LEPT emission and any LEPT-related transient absorption cannot be resolved in the solution phase. Accordingly, the reported triad system also does not provide clues to probe the correlation and/or relationship between PCET and PCEnT.\u003c/p\u003e\n\u003cp\u003eTo address this limitation and enable the observation of both CSS and LEPT emissions, it became imperative to design new analogues of\u003cstrong\u003e\u0026nbsp;triads 1\u0026ndash;8\u003c/strong\u003e. With this goal in mind, we strategically bridged the phenol and pyridine moieties of \u003cstrong\u003ePhOH-py\u003c/strong\u003e to develop a new triad, \u003cstrong\u003eAbPP,\u0026nbsp;\u003c/strong\u003ecomposed of an anthracene derivative and a bridged phenol-pyridine fragment. The structures of \u003cstrong\u003eAbPP\u003c/strong\u003e and its reference compounds, namely the bridged\u003cstrong\u003e\u0026nbsp;PhOH-py\u003c/strong\u003e (\u003cstrong\u003ebPP\u003c/strong\u003e), O\u003cstrong\u003e-\u003c/strong\u003emethylated \u003cstrong\u003ePhOH-py\u003c/strong\u003e (\u003cstrong\u003eOMe-bPP\u003c/strong\u003e), and O-methylated\u003cstrong\u003e\u0026nbsp;AbPP\u003c/strong\u003e (\u003cstrong\u003eOMe-AbPP\u003c/strong\u003e),\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eare depicted in\u0026nbsp;Scheme 1D. The bridged \u003cstrong\u003ebPP\u003c/strong\u003e of \u003cstrong\u003eAbPP\u003c/strong\u003e limits the torsional motion of LEPT, thereby bypassing the conical intersection. Consequently, both CSS and LEPT emissions of \u003cstrong\u003eAbPP\u003c/strong\u003e are observable under ambient conditions. This structural modification provides an avenue to experimentally validate PCEnT and explore its relationship with PCET, resolving key uncertainties in the field. Details of this investigation are elaborated in the following sections.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eProbe PCEnT in nonpolar solvents\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe success of the designed molecules was supported by the steady-state spectroscopic measurements, which were first performed in cyclohexane because its nonpolar nature minimizes solvation perturbations.\u0026nbsp;Therefore, the designed electron donor-acceptor triad\u0026nbsp;\u003cstrong\u003eA\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e, similar to the reported triads\u003csup\u003e1,6\u003c/sup\u003e, is expected to be PCET-free in cyclohexane to simplify the pursuit of PCEnT. First,\u0026nbsp;the 320 nm excitation of reference compound\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e in cyclohexane exhibits solely a large Stokes-shifted emission maximized at\u0026nbsp;~645 nm (Fig. 1A). In comparison,\u0026nbsp;\u003cstrong\u003eOMe\u003c/strong\u003e\u003cstrong\u003e-bPP\u003c/strong\u003e lacking O\u0026ndash;H protons shows\u0026nbsp;normal Stokes-shifted emission at\u0026nbsp;~360 nm in cyclohexane (Fig. S22).\u0026nbsp;Unambiguously, we conclude the occurrence of ultrafast ESIPT in\u0026nbsp;\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e, resulting in a 645 nm proton-transfer tautomer emission. We then probe \u003cstrong\u003eA\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e emission by 410 nm excitation, where there is no absorption from the\u0026nbsp;\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e moiety (absorption onset at ~360 nm for\u003cstrong\u003e\u0026nbsp;bPP\u003c/strong\u003e,\u0026nbsp;Fig. 1A), to ensure that only\u0026nbsp;\u003cstrong\u003eCN-Ant\u0026nbsp;\u003c/strong\u003emoiety\u0026nbsp;is\u0026nbsp;excited. The results (Fig. 1A) show that in addition to the\u0026nbsp;\u003cstrong\u003eCN-Ant\u0026nbsp;\u003c/strong\u003e(locally excited state, LES)\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eemission in the 420-500 nm region,\u0026nbsp;\u003cstrong\u003eA\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u0026nbsp;\u003c/strong\u003ealso clearly exhibits a 645 nm emission band.\u0026nbsp;Upon monitoring at the 645 nm emission band, the excitation spectrum reveals the\u003cstrong\u003e\u0026nbsp;CN-Ant\u0026nbsp;\u003c/strong\u003evibronic signature in the 360\u0026ndash;420 nm region (Fig. S23), confirming that excitation of the\u0026nbsp;\u003cstrong\u003eCN-Ant\u003c/strong\u003e unit indeed yields the 645 nm emission.\u0026nbsp;In contrast, 410 nm excitation on\u0026nbsp;\u003cstrong\u003eOMe-A\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e that is unable to undergo proton transfer only shows blue\u0026nbsp;\u003cstrong\u003eCN-Ant\u003c/strong\u003e emission in the 420-500 nm region (see\u0026nbsp;Fig. 1B). We also performed concentration-dependent studies of\u0026nbsp;\u003cstrong\u003eA\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e and eliminated the possibility that the 645 nm emission originates from aggregation (see\u0026nbsp;Fig. S25-28).\u0026nbsp;These comparative studies, coupled with\u0026nbsp;the\u0026nbsp;spectral resemblance between the\u0026nbsp;\u003cstrong\u003eA\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e 645 nm band and\u0026nbsp;\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e tautomer emission, lead us to conclude that excitation at the\u0026nbsp;\u003cstrong\u003eCN-Ant\u0026nbsp;\u003c/strong\u003emoiety of\u0026nbsp;\u003cstrong\u003eA\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e results in the \u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e tautomer emission, thus providing clear spectroscopic evidence for the operation of PCEnT in\u0026nbsp;\u003cstrong\u003eA\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e.\u003c/p\u003e\n\u003cp\u003eWith the direct evidence of PCEnT provided, we then gained further insights into its relevant dynamics. For the reference compound \u003cstrong\u003ebPP\u003c/strong\u003e in cyclohexane, monitoring the proton transfer emission region of, e.g., 670 nm under 300 nm excitation (Fig. 1C) shows a fast, system-response-limited rising component (details of time-correlated single photon counting (TCSPC), see SI), accompanied by a population decay fitted to be ~36 ps. Further femtosecond fluorescence upconversion measurement gave an ultrafast rise time of tautomer of 176 fs after convoluted with the system response of 120 fs (see inset of Fig. 1C). On the other hand, in cyclohexane, upon 410 nm excitation on the \u003cstrong\u003eCN-Ant\u003c/strong\u003e moiety of \u003cstrong\u003eAbPP\u003c/strong\u003e, time-resolved data monitoring at tautomer emission\u0026nbsp;clearly shows a rise and decay components fitted to be 36 ps and 136 ps, respectively (Fig. 1D). It is worth noting that the tautomer rise time of\u003cstrong\u003e\u0026nbsp;AbPP\u003c/strong\u003e is identical to the tautomer decay of \u003cstrong\u003ebPP\u003c/strong\u003e (Fig. 1C), while the tautomer decay of \u003cstrong\u003eAbPP\u003c/strong\u003e, within the fitting uncertainty, correlates well with the decay time (125 ps) of \u003cstrong\u003eCN-Ant\u003c/strong\u003e (see Fig. S29). From a kinetic perspective, this result is not surprising. It indicates that the PCEnT rate of \u003cstrong\u003eAbPP\u0026nbsp;\u003c/strong\u003eis significantly slower than the decay of the tautomer emission. Therefore, the kinetic derivation (see SI for details) clearly shows that the faster decay becomes the rising component, while the slower PCEnT becomes the decay component (Fig. 1E and 1F) of the proton-transfer tautomer emission. Accordingly, the PCEnT rate constant for\u003cstrong\u003e\u0026nbsp;AbPP\u0026nbsp;\u003c/strong\u003ein cyclohexane was concluded to be (125 ps)\u003csup\u003e-1\u003c/sup\u003e, yielding a proton-transfer tautomer emission with a decay lifetime of 36 ps. Using \u003cstrong\u003eAbPP\u003c/strong\u003e we therefore provide direct and unequivocal experimental evidence for PCEnT. Considering yielding the same proton transfer tautomer, the \u003cem\u003ek\u003csub\u003ePCEnT\u003c/sub\u003e\u003c/em\u003e = (125 ps)\u003csup\u003e-1\u003c/sup\u003eof \u003cstrong\u003eAbPP\u003c/strong\u003e in cyclohexane is three orders of magnitude slower than that of direct ultrafast ESIPT of \u003cstrong\u003ebPP\u0026nbsp;\u003c/strong\u003e((176 fs)\u003csup\u003e-1\u003c/sup\u003e), supporting that PCEnT is associated with a weak nonadiabatic coupling process\u003csup\u003e5\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eObserving emissions from PCEnT and PCET processes in polar solvents\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eEqually important as the evidence for PCEnT is to probe the relationship between PCEnT and PCET in polar solvents where PCET is expected to occur\u003csup\u003e1,6,12\u003c/sup\u003e. Fig. 2 shows the absorption and emission spectra of \u003cstrong\u003eA\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e in various solvents. Two excitation regions, 320 nm and 410 nm are applied here. The 320 nm excitation is primarily targeted at the \u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u0026nbsp;\u003c/strong\u003emoiety of \u003cstrong\u003eA\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e, which mainly undergoes direct, ultrafast ESIPT at a rate (~176 fs, see Fig. 1C) that exceeds all other excited-state relaxation pathways, leading to 645 nm tautomer emission band, the spectral feature of which is nearly independent of solvent polarity (see Fig. 2A, blue curves ). On the other hand, with 410 nm excitation that is exclusively on the \u003cstrong\u003eCN-Ant\u003c/strong\u003e moiety of \u003cstrong\u003eAbPP\u003c/strong\u003e, an emission band in the 600\u0026ndash;700 nm range was observed (Fig. 2A, black curves). A normalized zoom-in comparison with the emission excited at 320 nm revealed that the emission band under 410 nm excitation exhibited a red shift with increasing solvent polarity (Fig. 2B). Given that the proton-transfer tautomer spectral characteristics of direct ESIPT are nearly independent of solvent polarity (see Fig. 1A), this red-shifted emission band suggests the appearance of an additional longer-wavelength emission band in addition to the 645 nm tautomer emission. Although two bands cannot be distinctly separated due to the significant spectral overlap, the new band seems to increase in intensity and red-shifted with a trend of increasing polarity from dichloromethane (DCM), D7A1 (7:1 v/v DCM /acetonitrile (ACN)), to D6A1 (6:1 v/v DCM /ACN)) (Fig. 2B). In highly polar solvents such as ACN, both emissions decrease significantly and become obscure. Based on the CSS emission resolved from \u003cstrong\u003etriad 1\u003c/strong\u003e in this study\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e(Scheme 1C) and the fact that\u003cstrong\u003e\u0026nbsp;A\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e is a homolog of triads \u003cstrong\u003e1-8\u003c/strong\u003e (Scheme 1A), it is reasonable to assign the new band of \u003cstrong\u003eA\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u0026nbsp;\u003c/strong\u003ein polar solvents to the CSS emission generated by PCET. Relative to CSS, for convenience of discussion, the excited proton transfer tautomer of \u003cstrong\u003eA\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e is denoted as LEPT to be consistent with the previous assignment\u003csup\u003e1,6,12\u003c/sup\u003e. Despite the spectral overlap between CSS and LEPT emissions in \u003cstrong\u003eA\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e, their unique electronic characteristics enabled differentiation. The CSS emission exhibits solvatochromism due to its spatial charge separation, as shown in Scheme 1C for \u003cstrong\u003etriad 1\u003c/strong\u003e and Fig. 2 for \u003cstrong\u003eA\u003c/strong\u003e\u003cstrong\u003ebPP\u003c/strong\u003e. On the other hand, LEPT has elongated p-conjugation and minimal net charge transfer, for which the emission is essentially unaffected by the solvent polarity, as supported by the 645 nm peak wavelength in all studied solvents (Fig. 2). These findings confirm that the 410 nm excitation at the \u003cstrong\u003eCN-Ant\u003c/strong\u003e moiety of \u003cstrong\u003eA\u003c/strong\u003e\u003cstrong\u003ebPP\u003c/strong\u003e activates both PCEnT and PCET in room temperature polar solutions, giving LEPT and CSS emissions. However, despite the appropriate assignment, steady-state emission data alone do not illustrate the relationship between these two pathways. For example, are PCEnT and PCET in polar solvents following a sequential path? If so, what is the order of reaction? Or are they in parallel competing processes? Resolving this ambiguity requires gaining insights into their relaxation dynamics. Also, Fig. 2C presents the steady-state emission contributions of LEPT and CSS, with their deconvolution performed through kinetic analysis in the following section.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eKinetic expression of PCEnT and PCET\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eResolvable emission in each state allows us to apply femtosecond fluorescence upconversion and TCSPC methods to probe emission early relaxation dynamics and population decay, respectively. In this study, unless otherwise specified, the excitation wavelength was mainly fixed at 410 nm to excite the \u003cstrong\u003eCN-An\u003c/strong\u003et chromophore. The LES emission of \u003cstrong\u003eA\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e was monitored at 440 nm (the typical \u003cstrong\u003eCN-Ant\u0026nbsp;\u003c/strong\u003eemission), while CSS and LEPT emissions were monitored at \u0026gt; 600 nm to avoid any interference by the LES emission. The representative relaxation dynamics and relevant kinetic data of\u003cstrong\u003e\u0026nbsp;A\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e in DCM and D7A1 are depicted in Fig. 3. It is worth noting that the emission in ACN is shifted toward near-infrared and is of small intensity; therefore, the fluorescence upconversion data introduce large uncertainty. Alternatively, femtosecond transient absorption (TA) measurements were applied to probe the dynamics of CSS/LEPT in ACN (Fig. S34, see SI for detail).\u003c/p\u003e\n\u003cp\u003eAs shown in\u0026nbsp;Fig. 3A, the LES 440 nm emission\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eof \u003cstrong\u003eA\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e in DCM reveals a fast decay with a lifetime of 7.5 ps, which correlates well with 7.3 ps of the rise component monitored at emission at e.g., 700 nm. Extending the acquisition time through TCSPC method, the emission decay curve at \u0026gt;600 nm clearly consists of two components (Fig. 3B) with decay lifetime fitted to be 40 ps and 443 ps (Table 1). The intensity ratio of these two components depends on the emission wavelength, as demonstrated by the emission monitored at 600, 650, and 700 nm (see Fig. 3B and 3C). The results clearly support the emission at \u0026gt; 600 nm consisting of two excited-state species, most plausibly LEPT and CSS. In DCM, the lifetime\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eof proton-transfer tautomer emission of reference compound \u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e is determined to be 38 ps (see Table S3). Therefore, for \u003cstrong\u003eA\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e, it is reasonable to attribute the 40 ps decay component in DCM to the LEPT emission. Accordingly, the 443 ps component originates from the CSS emission. Furthermore, at the emission of \u0026gt; 600 nm, independent of the monitored wavelength, the rise component in DCM is fitted to be within 7.3 ps, which is equal to the decay time of the LES emission. The results indicate that both LEPT and CSS are populated from the same origin, i.e., the LES, but undergo different population decays. Briefly, under 410 nm excitation of \u003cstrong\u003eA\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e in DCM, the LES undergoes parallel PCEnT and PCET pathways at a total rate of (7.5 ps)\u003csup\u003e-1\u003c/sup\u003e, leading to LEPT and CSS emissions with a lifetime of 40 and 443 ps, respectively.\u0026nbsp;Similar relaxation kinetics for\u003cstrong\u003e\u0026nbsp;AbPP\u003c/strong\u003e were observed in other polar solvents, i.e., the rise time of LEPT and CSS was the same as the decay time of LES, while the decay times of LEPT and CSS were significantly different (Table 1). Furthermore, the intensity ratio of LEPT to CSS emissions showed emission wavelength dependence; the evidence is given by \u003cstrong\u003eAbPP\u003c/strong\u003e in DCM (Fig. 3B and 3C) and in D7A1 (Fig. 3E and 3F). Importantly, the sum of PCEnT and PCET rates increase with increasing the solvent polarity, which is in the order of (31.8 ps)\u003csup\u003e-1\u003c/sup\u003e in toluene \u0026lt; (7.5 ps)\u003csup\u003e-1\u003c/sup\u003e in DCM \u0026lt; (5.8 ps)\u003csup\u003e-1\u003c/sup\u003e in D7A1 \u0026lt; (2.8 ps)\u003csup\u003e-1\u003c/sup\u003e in ACN.\u003c/p\u003e\n\u003cp\u003eThe next issue that needs to be addressed is the branching ratio of PCEnT to PCET. Although the rates of PCEnT/PCET cannot be separated without knowing the individual product CSS and LEPT distribution, the PCET rate involving charge transfer must be strongly dependent on the solvent polarity, whereas PCEnT, as supported by the same emission peak wavelength and lifetime in various solvents, is expected to be solvent independent.\u0026nbsp;Therefore, it is reasonable to assume that the PCEnT rate in the solvents studied is similar, i.e., equivalent to the PCEnT rate of (125 ps)\u003csup\u003e-1\u003c/sup\u003e in cyclohexane. Consequently, the rates of PCET in toluene, DCM, D7A1, and ACN are deduced to be (42.6 ps)\u003csup\u003e-1\u003c/sup\u003e, (8.0\u0026nbsp;ps)\u003csup\u003e-1\u003c/sup\u003e, (6.1 ps)\u003csup\u003e-1\u003c/sup\u003e and (2.9 ps)\u003csup\u003e-1\u003c/sup\u003e, respectively, showing the trend of increasing PCET rate upon the increase of the solvent polarity. In other words, the PCET of \u003cstrong\u003eA\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e\u003cstrong\u003ePP\u003c/strong\u003e is in the Marcus normal region\u003csup\u003e1,6,12\u003c/sup\u003e. We then combined steady-state and kinetic results to deduce the contributions of CSS and LEPT in the steady-state emission spectra. In this approach, the emission ratios were analyzed by integrating kinetic decay curves to determine the intensity contribution at different monitoring wavelengths, where the decay curves were used to calculate the intensity ratio of CSS to LEPT emissions (see Fig. 3C and 3F in DCM and D7A1, respectively). The resulting data were then used as initial guesses for spectral fitting of the steady-state emission band between 600-800 nm in various solvents. Fig. 2C illustrates the evolution of the contribution ratio of CSS to LEPT emissions for \u003cstrong\u003eAbPP\u003c/strong\u003e in the studied solvents. The results clearly indicate that the LEPT state is minimally affected by solvent polarity, yielding a constant emission peak position at ~645 nm (blue shaded portion of Fig. 2C). In stark contrast, the CSS state, characterized by significant charge separation, exhibits a clear solvatochromism phenomenon (shaded red) with a peak wavelength red-shifted from 650 nm (in toluene) to the near-infrared region (in ACN, see inset of Fig. 2C). In ACN, the fast PCET (2.86 ps)\u003csup\u003e-1\u003c/sup\u003e leads to a small branching ratio of LEPT production. This, together with the NIR CSS emission that is subject to dominant radiationless quenching, gives obscure LEPT and CSS emissions in ACN.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eTable 1\u003c/strong\u003e The fitted rise and decay time constants of various emission components in \u003cstrong\u003eAbPP\u003c/strong\u003e under 410 nm excitation in various solvents.\u003c/p\u003e\n\u003cp\u003e\u003cimg 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\"\u003e\u003cbr\u003e\u003c/p\u003e\n\u003cp\u003e\u003cem\u003e\u003csup\u003ea.\u003c/sup\u003e\u003c/em\u003e D7A1 is mixture of DCM:ACN = 7:1 (v:v)\u003c/p\u003e\n\u003cp\u003e\u003cem\u003e\u003csup\u003eb\u003c/sup\u003e\u003c/em\u003e\u003csup\u003e.\u003c/sup\u003e Lifetimes measured using the TCSPC technique. \u003cem\u003e\u003csup\u003ec.\u003c/sup\u003e\u003c/em\u003e Lifetimes are measured using the upconversion technique. \u003cem\u003e\u003csup\u003ed.\u003c/sup\u003e\u003c/em\u003e Lifetimes measured using TA. For more details, refer to the supporting information.\u003c/p\u003e\n\u003cp\u003eAn important question that remains concerns the electron transfer between LEPT and CCS, which seems to be prohibited in \u003cstrong\u003eAbPP\u003c/strong\u003e due to two separate and distinct population decay times. If they were interconverted during the excited state lifetime, the same population decay would have been observed. We suspect that the failure of interconversion in \u003cstrong\u003eAbPP\u003c/strong\u003e is due to the rapid decay of LEPT emission (35-40 ps), which is governed by the deactivation of the partially flexible C\u003csub\u003e1\u003c/sub\u003e-C\u003csub\u003e1\u003c/sub\u003e\u0026rsquo; torsional motion (Scheme 1A). On the other hand, LEPT \u0026rarr; CCS charge transfer or vice versa (see Fig. 4) is expected to be much slower due to the larger spatial distance between donor and acceptor. From another perspective, the rates of PCEnT and PCET are faster than LEPT \u0026harr; CCS electron transfer in \u003cstrong\u003eAbPP\u003c/strong\u003e because both PCEnT and PCET simultaneously involve proton transfer that acts as a driving force to accelerate the reaction. Interestingly, if the LEPT emission lifetime is long enough, say a few nanoseconds, then interconversion between LEPT and CSS is expected to occur. This remains to be resolved by new triads in the future.\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eBy restricting, in part, the C\u003csub\u003e1\u003c/sub\u003e-C\u003csub\u003e1\u003c/sub\u003e’ torsional motion of \u003cb\u003ePhOH-py\u003c/b\u003e moiety in a newly designed triad, \u003cb\u003eAbPP\u003c/b\u003e, we reveal the spectroscopic signatures for both LEPT and CSS emissions in solution at room temperature. In nonpolar solvents such as cyclohexane, the excitation at the anthracene moiety (\u003cb\u003eCN-Ant\u003c/b\u003e) gives rise to the \u003cb\u003ebPP\u003c/b\u003e tautomer emission with a rate constant of (125 ps)\u003csup\u003e-1\u003c/sup\u003e, providing direct evidence for PCEnT. The rate of PCEnT is three orders of magnitude slower than direct ESIPT in bPP, which proceeds at ~ (176 fs)\u003csup\u003e-1\u003c/sup\u003e, highlighting the role of weak nonadiabatic coupling in facilitating PCEnT, in line with theoretical predictions.\u003csup\u003e5\u003c/sup\u003e. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e, PCEnT and PCET are concurrently two competitive reaction pathways, where the branching ratio for the rate of PCEnT to PCET decreases as increasing the solvent polarity. The CSS emission peak is strongly dependent on solvent polarity, shifting from 650 nm in toluene to approximately 1000 nm in ACN, accompanied by an increase in nonradiative quenching processes. These results establish a solid experimental framework for understanding PCEnT in ambient conditions and its interplay with PCET, providing a connection between these fundamental processes.\u003c/p\u003e \u003cp\u003eBeyond its mechanistic significance, our findings challenge the prevailing view that quantum processes are largely restricted to low temperatures. We show that PCEnT, which is an intrinsically quantum mechanical phenomenon, operates efficiently in room-temperature solutions, expanding the conceptual framework of energy transfer. The integration of electron, proton, and energy transfer in a single system has broad implications across biological, chemical, and optoelectronic contexts, paving the way for further exploration of quantum-driven reaction pathways under ambient conditions.\u003c/p\u003e "},{"header":"Method","content":"\u003cp\u003e \u003cb\u003eSynthesis.\u003c/b\u003e All reactions were performed under a nitrogen atmosphere unless otherwise noted. Solvents were distilled from appropriate drying agents prior to use. Commercially available reagents were used without further purification. Mass spectra were obtained on JEOL AccuTOF GCX instrument operating in field desorption (FD). \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz) and \u003csup\u003e13\u003c/sup\u003eC NMR (100 MHz) spectra were recorded on Bruker AVIII HD 400MHz NMR and Agilent Unity + 400MHz NMR. X-ray diffraction was conducted on Bruker AXS D8 VENTURE, PhotonIII_C28.\u003c/p\u003e\u003cp\u003e \u003cb\u003ePhotophysical Measurements.\u003c/b\u003e All photophysical measurements in this study, unless otherwise specified, were performed at room temperature (298 K). UV‒visible absorption spectra were recorded on a UV‒visible NIR spectrophotometer system (HITACHI UH5700). The steady-state emission spectra and excitation spectra were measured with a spectrofluorometer (Edinburgh FL 980). Both the wavelength-dependent excitation and emission responses were calibrated. The emission QY in solution was calculated using 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCMP) as a reference dye, for which the photoluminescence quantum yield (PLQY) is 44% in methanol\u003csup\u003e20\u003c/sup\u003e. All measurements were conducted using a 10-mm square cell unless otherwise noted.\u003c/p\u003e\u003cp\u003eSteady-state temperature-dependent fluorescence was also measured with a spectrofluorometer (Edinburgh FL 980). The temperature was set by a cryostat (Specac, P/N GS21525 DN1704) with a controller. An equilibration time of at least thirty minutes was supplied between temperatures, cooling the sample using N\u003csub\u003e2\u003c/sub\u003e(l), while maintaining a high vacuum within the chamber. The samples were contained within quartz (CFQ) EPR tubes – 5mm outer diameter, with concentration ~ 1.0 × 10\u003csup\u003e− 5\u003c/sup\u003e M.\u003c/p\u003e\u003cp\u003eThe picosecond time-resolved studies were performed by a time-correlated single photon counting (TCSPC) technique where a ~ 120 fs laser (410 and 300 nm) was used as a pumping source, which incorporated with a microchannel detector gives a time resolution of ~ 15 ps. As for the fluorescence upconversion measurement, a stable 120-fs LASER oscillator performed this ultrafast fluorescence upconversion measurement (FOG100-DX, CDP corp.). A PUMP beam of 410 and 300 nm was generated by the part of the oscillator output traveling through the second and third harmonic generation (SHG and THG, β-barium borate crystal). An iris selected the energy and the beam size of PUMP after this SHG and THG. The lens system was used to focus PUMP on the sample, to collect the fluorescence, and to focus the fluorescence on sum-frequency BBO crystal (SHG and THG, β-barium borate crystal), respectively. The entitled compounds are measured in a rotated cell with a transmitted collection mode. The GATE beam (820 and 900 nm) enters the delay line stage and crosses the fluorescence beam in the sum-frequency BBO with a collinear measurement. The polarized angle between PUMP and GATE is set at the magic angle (54.7˚). A monochromator was applied and coupled with a PMT to record the sum-frequency signal. In this research, the FWHM of IRF is ~ 150 fs.\u003c/p\u003e\u003cp\u003eFemtosecond transient absorption (fs-TA) setup of our light source is schematically illustrated in the previous work.\u003csup\u003e21\u003c/sup\u003e Briefly speaking, the measurements were performed using a commercial Yb: KGW laser system (Pharos, Light Conversion) with a central wavelength of 1030 nm, an average power of 2.5 W, a repetition rate of 3.125 kHz, a pulse energy of 800 µJ and a pulse duration of 190 fs. Two identical pulses were produced with a low-GDD 50/50 beam splitter and passed through our designed nonlinear compressor, named multiple plate compression (MPC). For this experiment, a high-pass filter with a cut-off wavelength of 980 nm was applied. Pulse compression was achieved with 8 chirped mirror bounces (Ultrafast Innovation), thus removing the material dispersion introduced by the optics before the sample. The compressed pulses had an FWHM duration of 3.2 fs and were characterized at the sample position with a polarization-gating frequency-resolved optical gating (PG-FROG).\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgments\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eWe acknowledge the Instrument Centre, National Taiwan University of Taiwan for the use of the facilities. We thank Mr.\u0026nbsp;Y.-H. Liu of Instrument Centre, National Taiwan University for the assistance in X-ray measurements.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis work was supported by\u0026nbsp;the National Science and Technology Council, R.O.C.\u003c/p\u003e\n\u003cp\u003eAcademia Sinica, Taiwan, AS-CDA-111-M02 to L.-Y.H.\u003c/p\u003e\n\u003cp\u003eNational Science and Technology Council, Taiwan, 111-2113-M-001-027-MY4 to L.-Y.H.\u003c/p\u003e\n\u003cp\u003ePhysics Division of the National Center for Theoretical Sciences, Taiwan, 112-2124-M-002-003 to L.-Y.H.\u003c/p\u003e\n\u003cp\u003eNational Science and Technology Council, Taiwan, 112-2113-M-002-011-MY3 to C.-T.C.\u003c/p\u003e\n\u003cp\u003eNational Science and Technology Council, Taiwan, 113-2639-M-002-001-ASP to P.-T.C.\u003c/p\u003e\n\u003cp\u003eThis research was also supported by the UMC Fellowship.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eP.\u0026nbsp;-T.\u0026nbsp;C. conceived the research and designed the experiments.\u003c/p\u003e\n\u003cp\u003eS. -F. W.,\u0026nbsp;C.\u0026nbsp;-Y.\u0026nbsp;L., Y.\u0026nbsp;-C.\u0026nbsp;C.,\u0026nbsp;and\u0026nbsp;Y.\u0026nbsp;-S.\u0026nbsp;T.\u0026nbsp;Y. executed the synthesis and characterization of all studied compounds and grew the corresponding crystals.\u003c/p\u003e\n\u003cp\u003eC. -P. H. conducted the cyclic voltammetry (CV) measurement of designed samples.\u003c/p\u003e\n\u003cp\u003eY.\u0026nbsp;-Y.\u0026nbsp;T., C. -H. W.,\u0026nbsp;H.\u0026nbsp;-T.\u0026nbsp;Q., and C. -H. H. conducted optical measurements and analyzed the data.\u003c/p\u003e\n\u003cp\u003eY. -C. W.,\u0026nbsp;Y.\u0026nbsp;-C.\u0026nbsp;C.,\u0026nbsp;L. -Y. H.,\u0026nbsp;C.\u0026nbsp;-T.\u0026nbsp;C., and P.\u0026nbsp;-T.\u0026nbsp;C. supervised the project.\u003c/p\u003e\n\u003cp\u003eC.\u0026nbsp;-H.\u0026nbsp;W., Y.\u0026nbsp;-Y.\u0026nbsp;T.,\u0026nbsp;and P.\u0026nbsp;-T.\u0026nbsp;C. wrote the manuscript.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData and materials availability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAll data are available in the main text or the supplementary materials.\u003c/p\u003e"},{"header":" References","content":"\u003col\u003e\n\u003cli\u003ePettersson Rimgard, B.\u003cem\u003e et al.\u003c/em\u003e Proton-coupled energy transfer in molecular triads. \u003cem\u003eScience\u003c/em\u003e \u003cstrong\u003e377\u003c/strong\u003e, 742-747 (2022). \u003c/li\u003e\n\u003cli\u003eF\u0026ouml;rster, T. Zwischenmolekulare Energiewanderung und Fluoreszenz. \u003cem\u003eAnn. Phys.\u003c/em\u003e \u003cstrong\u003e437\u003c/strong\u003e, 55-75 (1948). \u003c/li\u003e\n\u003cli\u003eSilbey, R. Electronic energy transfer in molecular crystals. \u003cem\u003eAnnu. Rev. Phys. Chem.\u003c/em\u003e \u003cstrong\u003e27\u003c/strong\u003e, 203-223 (1976).\u003c/li\u003e\n\u003cli\u003eScholes, G. D. Long-range resonance energy transfer in molecular systems. \u003cem\u003eAnnu. Rev. Phys. Chem.\u003c/em\u003e \u003cstrong\u003e54\u003c/strong\u003e, 57-87 (2003).\u003c/li\u003e\n\u003cli\u003eCui, K. \u0026amp; Hammes-Schiffer, S. Theory for proton-coupled energy transfer. \u003cem\u003eJ. Chem. Phys.\u003c/em\u003e \u003cstrong\u003e161\u003c/strong\u003e (2024).\u003c/li\u003e\n\u003cli\u003eParada, G. 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R.\u003cem\u003e et al.\u003c/em\u003e Proton-Coupled Electron Transfer. \u003cem\u003eChem. Rev.\u003c/em\u003e \u003cstrong\u003e112\u003c/strong\u003e, 4016-4093 (2012).\u003c/li\u003e\n\u003cli\u003eHsieh, C.-C., Jiang, C.-M. \u0026amp; Chou, P.-T. Recent Experimental Advances on Excited-State Intramolecular Proton Coupled Electron Transfer Reaction. \u003cem\u003eAcc. Chem. Res.\u003c/em\u003e \u003cstrong\u003e43\u003c/strong\u003e, 1364-1374 (2010).\u003c/li\u003e\n\u003cli\u003eBowring, M. A.\u003cem\u003e et al.\u003c/em\u003e Activationless multiple-site concerted proton\u0026ndash;electron tunneling. \u003cem\u003eJ. Am. Chem. Soc.\u003c/em\u003e \u003cstrong\u003e140\u003c/strong\u003e, 7449-7452 (2018).\u003c/li\u003e\n\u003cli\u003eCotter, L. F.\u003cem\u003e et al.\u003c/em\u003e Evidence for Competing Proton-Coupled Reaction Pathways of Molecular Triads in a Low-Polarity Solvent. \u003cem\u003eJ. Phys. Chem. 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Photobiol., A\u003c/em\u003e \u003cstrong\u003e117\u003c/strong\u003e, 209-216 (1998).\u003c/li\u003e\n\u003cli\u003eKim, S., Seo, J. \u0026amp; Park, S. Y. Torsion-induced fluorescence quenching in excited-state intramolecular proton transfer (ESIPT) dyes. \u003cem\u003eJ. Photochem. Photobiol., A\u003c/em\u003e \u003cstrong\u003e191\u003c/strong\u003e, 19-24 (2007).\u003c/li\u003e\n\u003cli\u003eMartinez, M. L., Cooper, W. C. \u0026amp; Chou, P.-T. A novel excited-state intramolecular proton transfer molecule, 10-hydroxybenzo[h]quinoline. \u003cem\u003eChem. Phys. Lett.\u003c/em\u003e \u003cstrong\u003e193\u003c/strong\u003e, 151-154 (1992).\u003c/li\u003e\n\u003cli\u003eChou, P.-T. \u0026amp; Martinez, M. L. Photooxygenation of 3-hydroxyflavone and molecular design of the radiation-hard scintillator based on the excited-state proton transfer. \u003cem\u003eRadiat. Phys. 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Ed.\u003c/em\u003e \u003cstrong\u003e62\u003c/strong\u003e, e202300815 (2023).\u003c/li\u003e\n\u003cli\u003eLian, X.\u003cem\u003e et al.\u003c/em\u003e Siteselective and Enantiocomplementary C(sp3)\u0026ndash;H Oxyfunctionalization for Synthesis of \u0026alpha;-Hydroxy Acids. \u003cem\u003eACS Catal.\u003c/em\u003e \u003cstrong\u003e14\u003c/strong\u003e, 4463-4470 (2024).\u003c/li\u003e\n\u003cli\u003eCastillo-Rangel, N., P\u0026eacute;rez-D\u0026iacute;az, J. O. H. \u0026amp; V\u0026aacute;zquez, A. An Expeditious Synthesis of 8-Methoxy-1-tetralone. \u003cem\u003eSynth.\u003c/em\u003e \u003cstrong\u003e48\u003c/strong\u003e, 2050-2056 (2016).\u003c/li\u003e\n\u003cli\u003eOkamoto, K., Watanabe, M., Murai, M., Hatano, R. \u0026amp; Ohe, K. Practical synthesis of aromatic nitrilesviagallium-catalysed electrophilic cyanation of aromatic C\u0026ndash;H bonds. \u003cem\u003eChem. Commun.\u003c/em\u003e \u003cstrong\u003e48\u003c/strong\u003e, 3127-3129 (2012).\u003c/li\u003e\n\u003c/ol\u003e"},{"header":"Scheme","content":"\u003cp\u003eScheme 1 is available in the Supplementary Files section.\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":false,"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-6244115/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6244115/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eProton-coupled energy transfer (PCEnT) is new\u003csup\u003e1\u003c/sup\u003e and differs from traditional energy transfer in that there is virtually no ground-state tautomer population, but energy transfer can still occur by simultaneously coupling the proton transfer. PCEnT should herald a revolutionary photochemical breakthrough. However, despite theoretical advancement\u003csup\u003e2\u003c/sup\u003e, so far, the only PCEnT-related experiment was performed under an extreme environment (77K glass matrix) with complexity\u003csup\u003e1\u003c/sup\u003e. Herein, utilizing a new molecular triad \u003cb\u003eAbPP\u003c/b\u003e comprising anthracene and bridged phenolpyridine, we provide direct and unambiguous experimental evidence for PCEnT in the room temperature solution for the first time. In cyclohexane, the rate of PCEnT for \u003cb\u003eAbPP\u003c/b\u003e is measured to be (125 ps)\u003csup\u003e-1\u003c/sup\u003e, which is three orders of magnitude slower than the rate of direct excited-state intramolecular proton transfer (ESIPT)((176 fs)\u003csup\u003e-1\u003c/sup\u003e) but yields the same 645 nm proton transfer isomer emission, supporting a weak nonadiabatic coupling process for PCEnT. This result challenges the traditional assumption that quantum processes manifest primarily at low temperatures, as it demonstrates that PCEnT\u0026mdash;a fundamentally quantum mechanical mechanism\u0026mdash;can occur efficiently in room-temperature solutions. Equally important, the resolved emission of proton-transfer tautomers and charge-separated states produced by PCEnT and proton-coupled electron transfer (PCET), respectively, allows for comprehensive probing of the correlation between PCEnT and PCET, with the increase of PCET rates upon increasing solvent polarity. These findings diversify the interplay among electron, proton, and energy transfer, the three fundamental mechanisms of chemical transformations.\u003c/p\u003e","manuscriptTitle":"Room Temperature Proton Coupled Energy Transfer","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-05-29 06:13:36","doi":"10.21203/rs.3.rs-6244115/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"communications-chemistry","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"commschem","sideBox":"Learn more about [Communications Chemistry](http://www.nature.com/commschem/)","snPcode":"","submissionUrl":"","title":"Communications Chemistry","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Communications Series","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"88c9f082-55b3-4934-8332-e86faf75f92b","owner":[],"postedDate":"May 29th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[{"id":49130223,"name":"Physical sciences/Chemistry/Physical chemistry/Energy transfer"},{"id":49130224,"name":"Physical sciences/Chemistry/Physical chemistry/Electron transfer"}],"tags":[],"updatedAt":"2025-08-27T08:40:24+00:00","versionOfRecord":[],"versionCreatedAt":"2025-05-29 06:13:36","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-6244115","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6244115","identity":"rs-6244115","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}