Modulation of Conjugation Pathways and Charge Transport in Supramolecular Semiconductors via Hydrogen-Bonding Topology

Modulation of Conjugation Pathways and Charge Transport in Supramolecular Semiconductors via Hydrogen-Bonding Topology | 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 Research Article Modulation of Conjugation Pathways and Charge Transport in Supramolecular Semiconductors via Hydrogen-Bonding Topology Raúl González-Núñez, Gabriel Martínez, Kyeong-Im Hong, Wakana Matsuda, and 4 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8657581/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Precise control over conjugation pathways is essential for the development of high-performance organic semiconductors, particularly in hydrogen-bonded systems where subtle structural variations can strongly influence molecular planarity, supramolecular organization, and charge transport. Here, we demonstrate that the relative positioning of hydrogen-bonding motifs with respect to a π-conjugated core enables the modulation of conjugation pathways through controlled intra- or intermolecular hydrogen-bonding. A series of thiophene-capped diketopyrrolopyrrole (DPP) small molecules bearing amide functionalities at well-defined distances from the conjugated backbone was designed to selectively favor distinct hydrogen-bonding topologies. A combined experimental and theoretical approach, including density functional theory calculations, vibrational and electronic spectroscopies, electrochemistry, and solid-state characterization, reveals that proximal amide groups favor intramolecular hydrogen-bonding that disrupts backbone planarity and limits effective π-conjugation. In contrast, distal amide placement promotes intermolecular hydrogen-bonding involving the DPP carbonyl groups, leading to extended conjugation pathways and enhanced supramolecular organization in the solid state. This modulation of hydrogen-bond topology results in markedly different charge-carrier dynamics and transport characteristics, as evidenced by electrodeless photoconductivity measurements and organic field-effect transistor devices. Overall, this work establishes hydrogen-bond topology, rather than hydrogen-bonding alone, as a key molecular design parameter for the modulation of conjugation extension and charge transport in hydrogen-bonded small-molecule semiconductors, providing general insights for the rational design of functional supramolecular electronic materials. Organic Chemistry Materials Chemistry Electronic Materials and Devices Hydrogen-bonding conjugation modulation organic semiconductors supramolecular assembly charge transport Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Introduction In the rapidly evolving field of organic semiconductors, hydrogen-bonded materials have emerged as a class of compounds with promising electronic properties and tuneable functionalities. 1–6 Within this broad class of materials, small molecules that integrate π-conjugated cores with hydrogen-bonding motifs are of particular interest due to their structural versatility and potential in electronic applications. 2,7,8 In these systems, intra- and intermolecular hydrogen-bonding can significantly influence molecular planarity, effective π-conjugation length, and solid-state organization, all of which are critical parameters governing charge transport. 9–12 In this sense, a key design challenge lies in modulating hydrogen-bonding patterns to favor extended conjugation pathways that facilitate or block the generation of charge carriers, altering the final electrical performance. In particular, hydrogen-bonding may involve either pendant functional groups or the conjugated backbone itself, potentially altering conjugation pathways by favoring or suppressing specific electronic couplings. Despite its importance, the role of hydrogen-bond topology, that is, whether hydrogen-bonding occurs intra- or intermolecularly and how it engages the π-conjugated core, remains insufficiently understood, especially in small-molecule semiconductors. A central challenge in the rational design of hydrogen-bonded semiconductors is therefore not merely the introduction of hydrogen-bonding motifs, but the controlled modulation of conjugation pathways through precise molecular design. In this context, intramolecular-hydrogen-bonding may rigidify molecular conformations or, conversely, induce backbone distortion, while intermolecular hydrogen-bonding can promote supramolecular order and electronic delocalization across neighboring molecules. Disentangling these competing effects requires molecular systems in which hydrogen-bonding topology can be systematically tuned without altering the electronic nature of the conjugated core. Diketopyrrolopyrrole (DPP) derivatives represent an ideal platform to address this challenge. DPP-based small molecules are well known for their strong light absorption, high charge-carrier mobilities, and structural robustness, and their electronic properties are highly sensitive to backbone planarity and intermolecular interactions. 13,14 Recently, hydrogen-bonding has been successfully exploited in DPP-based materials to enhance charge transport, improve air stability, and control self-assembly.³ , ⁵ , ⁶ Nevertheless, the specific consequences of engaging the DPP carbonyl groups in hydrogen-bonding, particularly in distinguishing intra- versus intermolecular interactions, have only begun to be explored. In our recent work, we demonstrated that a thiophene-capped DPP derivative bearing distal amide groups exhibits superior charge-transport properties compared to a non-hydrogen-bonding analogue.¹⁵ Notably, the enhanced performance was attributed not only to supramolecular aggregation, but to a specific intermolecular hydrogen-bond between the DPP carbonyl and a pendant amide of a neighboring molecule. This interaction favored a linear thiophene–DPP–thiophene conjugation pathway while suppressing a competing cross-conjugated route involving the DPP carbonyls, highlighting hydrogen-bonding as an effective lever to modulate conjugation pathways. 15 Here, we build on this concept and investigate how the distance between hydrogen-bonding motifs and the conjugated DPP core governs hydrogen-bond topology, molecular planarity, and electronic properties. To this end, we design and synthesize a series of thiophene-capped DPP small molecules bearing amide functionalities positioned at precisely defined distances from the π-conjugated backbone, namely HDPPBA-2C , HPDDBA-4C and HDPPBA-6C (Fig. 1 a). This molecular design allows selective promotion of either intramolecular or intermolecular hydrogen-bonding while preserving the electronic identity of the conjugated core. For comparison, we have included as well a control molecule, HDPPBA (Fig. 1 a) unable to form hydrogen-bonds, that was previously synthesized and reported by us. 16 Through a combined experimental and theoretical approach, including density functional theory calculations (DFT), UV–vis and vibrational spectroscopies, electrochemistry, electrodeless photoconductivity measurements, atomic force microscopy, and organic field-effect transistor (OFET) characterization, we demonstrate that hydrogen-bond topology plays a decisive role in the modulation of conjugation pathways and charge transport. Intriguingly, we observe deviations from previously reported conjugation mechanisms, finding a new role for intramolecular hydrogen-bonding in shaping the electronic landscape of these materials. Proximal amide groups favor intramolecular hydrogen-bonding that disrupts backbone planarity and limits effective π-conjugation, whereas distal amide placement promotes intermolecular hydrogen-bonding, enhanced supramolecular organization, and improved charge transport. Although this study focuses on DPP-based semiconductors, the underlying design principle, specifically the modulation of conjugation pathways through controlled hydrogen-bond topology, is broadly applicable to other hydrogen-bonded π-conjugated small molecules and supramolecular semiconductors. Together, our results hold significance for the development of efficient organic semiconductor materials but also contribute to the broader understanding of the role of hydrogen-bonding in shaping the electronic properties of functional molecular systems, even those based on particularly small molecules. Ultimately, these findings aim to provide valuable insights that can guide the rational design of hydrogen-bonded semiconductors, opening new avenues for the progress of organic optoelectronics. Results and discussion Synthesis Compounds 1 and HDPPBA-6C were synthesized following a protocol previously reported by our group. 16 On the other hand, HDPPBA-2C and HDPPBA-4C were obtained starting from derivative 1 , and introducing the hydrogen-bonding motifs in subsequent steps (Scheme S1). 16 Initially, product 1 was alkylated using t -butyl bromoacetate and t -butyl 4-bromobutanoate to afford HDPP-2C-P and HDPP-4C-P in 17% and 13% yield, respectively. 17 The low yields are attributed to the reduced solubility of the starting material 1 in acetone, in addition to the expected formation of N,O - and/or O,O’ - alkylated isomers as byproducts. 18 Then, a deprotection step was performed using trifluoroacetic acid (TFA) to isolate HDPP-2C-acid and HDPP-4C-acid with 78% and 89% yield, respectively. Finally, the resulting diacids were functionalized with 1-decanamine and 1-octanamine through a peptide coupling reaction using hexafluorophosphate benzotriazole tetramethyl uronium (HBTU) 19 to obtain HDPPBA-2C and HDPPBA-4C in 79 and 89% yields, respectively (Scheme S1). The final molecules were characterized by 1 H, 13 C-NMR and high-resolution mass spectrometry (see SI for detailed description and full characterization). Structural and optical properties To elucidate how hydrogen-bond topology influences molecular structure and effective π-conjugation, ground-state density functional theory (DFT) calculations were performed on the amide-functionalized DPP derivatives. The optimized geometries reveal a pronounced dependence of backbone planarity on the relative position of the amide groups with respect to the conjugated core HDPPBA-4C and HDPPBA-6C adopt nearly fully planar conformations, with dihedral angles close to 0° between the DPP core and the flanking thiophene units (Fig. 1 b). This planarity is stabilized by weak intramolecular O–H interactions between the DPP carbonyl oxygen and the adjacent thiophene hydrogen atoms, which effectively lock the thiophene–DPP–thiophene backbone in a coplanar geometry (Fig. 1 b and Figure S1 for HDPPBA-4C ). The calculated O-H distance is 2.1 Å, lower than the sum of the Van der Waals radii (2.72 Å), corroborating the aforementioned interactions. In contrast, HDPPBA-2C exhibits a significantly distorted backbone, with dihedral angles of approximately 15° between the DPP and thiophene units. In this case, the proximity of the amide groups enables the formation of intramolecular hydrogen-bonds between the amide N–H and the DPP carbonyl oxygen, suppressing the stabilizing O–H interactions observed in the longer-spacer derivatives and inducing backbone twisting (Fig. 1 c). These structural differences have direct consequences for the electronic structure. The energies and topologies of the studied compounds were also predicted (Fig. 2 and Figure S2). As expected, the frontier molecular orbitals in the three studied molecules are delocalized over the whole conjugated skeleton with a greater contribution on the DPP core. DFT calculations point out quite similar Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) energy levels for HDPPBA-4C and HDPPBA-6C , with energy gaps of 2.41–2.42 eV, very similar to those of the control HDPPH . On the contrary, in HDPPBA-2C , both HOMO and LUMO energy levels are stabilized with respect to those of HDPPBA-4C and HDPPBA-6C , in around 0.3–0.41 eV in the case of the LUMO level and 0.36–0.46 for the HOMO level. Thus, the theoretical energy gap is slightly enlarged, being 2.47 eV for HDPPBA-2C . This is ascribed to the planarity loss due to the hydrogen-bond intramolecular interactions. Together, the DFT results establish that hydrogen-bond topology controls molecular planarity and π-conjugation, providing a structural basis for the distinct electronic and transport properties observed experimentally. The influence of hydrogen-bond topology on the optical properties of the DPP derivatives was investigated by UV–vis absorption spectroscopy in solution and in thin films (Fig. 3 ). The results were rationalized with the help of the time-dependent density functional theory (TD-DFT) (Figure S3). In dilute chloroform solutions, all three derivatives as well as the control molecule exhibit similar absorption spectra, characterized by two intense bands typical of DPP chromophores, having absorption maxima around λ = 520 nm and λ = 560 nm (Fig. 3 a-d, black traces). Although the overall spectra are similar across the series, HDPPBA-2C shows a slight blue-shift of the absorption maxima compared to HDPPBA-4C and HDPPBA-6C . This subtle difference is consistent with reduced backbone planarity and shorter effective conjugation length in HDPPBA-2C , in agreement with DFT predictions. The lowest-energy absorption, assigned to a single electron HOMO→LUMO transition, 20 appears at comparable wavelengths for the three compounds, reflecting the limited extent of hydrogen-bonding under these conditions due to good solubility and low aggregation. In thin films (Fig. 3 a-d, red traces), the absorption spectra broaden and red-shift relative to solution, with main bands around 490 and 610 nm, indicating enhanced intermolecular interactions and solid-state organization. However, despite the resemblance between the spectra of the three studied molecules, UV-Vis absorption spectra already account for the skeleton planarity loss in HDPPBA-2C , since both solution and film UV-Vis maxima are slightly blue-shifted respect those of HDPPH, HDPPBA-4C and HDPPBA-6C . These results indicate that differences in hydrogen-bond topology primarily manifest in the solid state, where molecular packing and supramolecular organization amplify their electronic consequences. Vibrational Spectroscopic analysis Vibrational spectroscopy was employed to experimentally identify hydrogen-bond formation and assess its impact on molecular conjugation in the solid state. Attenuated total reflectance infrared (ATR-IR) spectra of the stretching vibration of the C = O group (ν(C = O)), reveal two distinct C = O stretching contributions for the amide-functionalized derivatives, corresponding to the carbonyl group in the DPP core and the pendant amide groups (Fig. 4 a, see the eigenvectors in Figure S4). HDPPH displays a unique IR band at 1656 cm − 1 (Fig. 4 a), helping us to identify the ν(C = O) of the DPP core in the HDPPBA derivatives. Therefore, the DPP ν (C = O) IR band is recorded at 1653 cm − 1 , 1659 cm − 1 and 1657 cm − 1 for HDPPBA-2C , HDPPBA-4C and HDPPBA-6C , respectively (Fig. 4 a). While the DPP carbonyl stretching frequency remains nearly invariant across the series, with a subtle downshift found in HDPPBA-2C , the amide C = O vibration exhibits a pronounced downshift for HDPPBA-4C and HDPPBA-6C (1642 cm − 1 ) relative to HDPPBA-2C (1670 cm − 1 ). This downshift is indicative of strong hydrogen-bond engagement of the amide carbonyls in the longer-spacer derivatives, consistent with intermolecular hydrogen-bonding. In contrast, the higher-frequency amide C = O stretching observed for HDPPBA-2C suggests the absence of strong intermolecular interactions involving the amide group. Theoretical DFT calculations (Fig. 4 b and Figure S5) predict this IR band at around 1710 cm − 1 , which is consistent with the position found for HDPPBA-2C . Thus, ATR-IR data points out to the formation of hydrogen-bonding interactions in HDPPBA-4C and HDPPBA-6C , due to the enlargement of the C = O bond of the amide group. Analysis of the N–H stretching region further supports this assignment (Fig. 4 c and 4 d). Experimental spectra show hydrogen-bonded N–H vibrations for all three compounds. However, DFT calculations (Fig. 4 d) predict significant N–H red-shifting only for HDPPBA-2C (3381 cm − 1 ), consistent with intramolecular hydrogen-bonding that can be captured at the single-molecule level (Fig. 4 d), while for HDPPBA-4C and HDPPBA-6C that IR vibration is predicted at much higher wavenumbers (∼3500 cm − 1 ), characteristic of free amides (Fig. 4 d). These results indicate that the three compounds are involved in hydrogen-bonding interactions but of different nature. Thus, HDPPBA-4C and HDPPBA-6C form intermolecular hydrogen-bonding interactions, while the nature of such interactions in HDPPBA-2C is of intramolecular character, between the N-H group of the amide unit and the C = O group of the DPP unit, since theoretical calculations of a single molecule in vacuum are able to predict the interaction. The different nature of the hydrogen-bonds in HDPPBA-4C and HDPPBA-6C versus HDPPBA-2C also explains the subtle downshift of the ν (C = O) vibration of the DPP group in the latter, which is, in that case, involved in the intramolecular interaction and the upshift of the ν (C = O) vibration of the amide, being free of interaction (Fig. 4 a). Complementary insight into conjugation is provided by Raman spectroscopy, which probes the collective ν (C = C/C-C) vibration along the thiophene–DPP–thiophene backbone (Fig. 5 , see eigenvectors in Figure S6 and theoretical calculated spectra in Figure S7). This Raman vibration is recorded at 1528 cm − 1 for HDPPH (Fig. 5 ), while it is slightly upshifted (1534 cm − 1 ) for HDPPBA-2C (Fig. 5 ), which is an indicative of the loss of planarity due to the formation of intramolecular hydrogen-bond interactions, as seen above. On the contrary, the position of this Raman band in HDPPBA-6C , HDPPBA-4C , where intermolecular hydrogen-bonds are present, is comparable to that of the control molecule (1528 cm − 1 ) but with a clear widening (Fig. 5 ). Thus, two different contributions at 1526–1527 cm − 1 and 1530 cm − 1 are found, indicative of the coexistence of various conjugation paths. This has been previously analyzed by our group 15 and is ascribed to some participation of the carbonyl group of the DPP unit in the supramolecular hydrogen-bond interactions, favoring π-conjugation extension. Overall, vibrational spectroscopy corroborates the DFT results and demonstrates that hydrogen-bond topology governs both backbone planarity and effective conjugation in the solid state. Electrochemical study Cyclic voltammetry measurements in solution (1 mM in CH 2 Cl 2 ) reveal similar redox behaviour for all three derivatives, with two one-electron oxidation processes and two reduction process observed within comparable potential windows (Figure S8 and Table S1). The HOMO and LUMO energy levels were calculated from the oxidation and reduction onset potentials, respectively and using ferrocene as a reference (Table S1). The HOMO levels of HDPPH , HDPPBA-2C , HDPPBA-4C and HDPPBA-6C were calculated to be -5.1, -5.14, -5.1 and − 5.09 eV, correspondingly. The modest shifts in oxidation potentials, with HDPPBA-2C displaying slightly higher values, are consistent with its reduced backbone planarity and stabilized frontier orbitals predicted by DFT. On the other hand, the obtained LUMO values were − 3.37, -3.39, -3.34 and − 3.37 eV (See SI for details on the HOMO and LUMO calculations). The four derivatives have similar band gaps, being 1.73 eV, 1.75 eV, 1.76 eV and 1.72 eV for HDPPBA-2C , HDPPBA-4C and HDPPBA-6C , respectively. Importantly, the overall similarity of the solution-phase electrochemistry indicates that the intrinsic redox properties of the isolated molecules are largely unaffected by the position of the amide groups under these conditions, where hydrogen-bonding and aggregation are negligible. CV experiments in thin films drop cast from CH 2 Cl 2 solutions were performed using acetonitrile to dissolve TBAPF 6 as the supporting electrolyte (Fig. 6 , Figure S9 and Table S2). Cyclic voltammetry performed on drop-cast thin films reveals marked differences in the electrochemical response as a function of hydrogen-bond topology. While all derivatives exhibit oxidation features characteristic of DPP-based semiconductors, the voltammograms of HDPPBA-4C and HDPPBA-6C display broader oxidation waves with partially overlapping oxidation bands compared to HDPPBA-2C . This behaviour is indicative of a larger population of electroactive sites and enhanced charge delocalization in the solid state. In contrast, HDPPBA-2C shows comparatively sharper and less intense redox features, consistent with a more localized oxidation process. The HOMO levels of HDPPH , HDPPBA-2C , HDPPBA-4C and HDPPBA-6C were calculated to be -5.63, -5.57, -5.48 and − 5.56 eV, correspondingly. The obtained LUMO values were − 3.74, -3.88, -3.83 and − 3.87 eV for HDPPH , HDPPBA-2C , HDPPBA-4C and HDPPBA-6C , respectively. The energy band gaps for the hydrogen-bonded derivatives are similar, ranging from 1.66 eV for HDPPBA-4C to 1.69 eV for HDPPBA-2C and HDPPBA-6C . Despite the similar energy band gaps, the positioning of the HOMO levels shows slightly higher energy for HDPPBA-2C as a result of the loss of planarity and more difficult oxidation. These trends agree with our previous findings on thiophene-capped DPP derivatives, where intermolecular hydrogen-bonding involving the DPP carbonyl groups was shown to promote extended conjugation pathways and stabilize charged species in the solid state. 15 In the present series, the distal positioning of the amide groups in HDPPBA-4C and HDPPBA-6C favours intermolecular hydrogen-bond formation, facilitating electronic communication between neighbouring molecules and leading to electrochemically stabilized oxidized states. Conversely, the predominance of intramolecular hydrogen-bonding in HDPPBA-2C disrupts backbone planarity and limits intermolecular electronic coupling. Analysis of electronic properties by spectroelectrochemistry. Charge carriers’ stabilization. In order to evaluate the ability of the studied semiconductors to stabilize charge carriers and to probe if the differences in hydrogen-bonding topology plays a role in the formation of charged species, we performed in situ spectroelectrochemical studies in dilute dichloromethane solution (10 -4 M) at room temperature using 0.1M Bu 4 NPF 6 as supporting electrolyte and an optically transparent thin-layer electrochemical (OTTLE) cell, as well as TD-DFT calculations to support the experimental results. As shown in Figures S10-S13, HDPPBA-2C , HDPPBA-4C , HDPPBA-6C as well as the control HDPPH behave similarly in solution and able to stabilize one positive charge. The similar behaviour is expected due to the absence or minimization of intermolecular interactions in dilute solutions. Nevertheless, the distortion of the conjugated skeleton of HDPPBA-2C due to the formation of intramolecular hydrogen-bonds, results in much higher potentials needed to stabilize the charges (Figures S10 to S13). Electrical studies To directly probe charge-carrier dynamics in the solid state, electrodeless photoconductivity measurements were performed using Flash-Photolysis Time-Resolved Microwave Conductivity (FP-TRMC) 21,22 on thin films of the three hydrogen-bonded derivatives prepared by drop casting CHCl 3 solutions of the DPP derivatives. This technique provides a measure of photoconductivity as ΦΣ µ , where Φ is the charge carrier generation quantum yield and Σ µ is the sum of charge carrier mobilities of electrons and holes (See the SI for the measurement details). The thin films are irradiated with a pulsed laser generating charge carriers, being possible to follow their lifetimes before recombination. The kinetic traces of conductivity transients are shown in Fig. 7 , and the calculated values of photoconductivity (ϕΣ µ ), rate constants ( k , calculated 3 µs after pulse excitation) and half lifetime ( t 1/2 ) are summarized in Table 1 . All compounds exhibit measurable photoconductivity, ranging from 1.5 to 3.5 x 10 − 5 cm 2 V –1 s –1 (Table 1 ), being HDPPBA-2C the derivative with the lowest photoconductivity value. Interestingly, remarkable differences emerge in charge-carrier lifetimes. HDPPBA-4C and HDPPBA-6C display significantly longer carrier lifetimes up to one order of magnitude higher than HDPPBA-2C , which has charge carrier lifetime values in the same order as HDPPH unable to form hydrogen-bonds. 16 This indicates that while charge generation efficiencies are similar, charge stabilization and transport are markedly less effective in HDPPBA-2C . This trend mirrors the thin-film CV results. In HDPPBA-4C and HDPPBA-6C , the presence of hydrogen-bond-stabilized electroactive populations facilitates not only charge formation but also charge persistence, consistent with delocalized conjugation pathways and interconnected supramolecular networks. In contrast, the uniform but intramolecularly hydrogen-bonded environment of HDPPBA-2C enables oxidation but fails to support long-lived, mobile charge carriers. Atomic force microscopy provides a structural basis for these observations (Fig. 8 ). HDPPBA-4C and HDPPBA-6C form dense, interconnected fibrillar networks, providing continuous pathways for charge transport. In contrast, HDPPBA-2C self-assembles into shorter, poorly connected domains, which act as barriers to long-range charge migration and promote rapid recombination. Thus, FP-TRMC and AFM together demonstrate that hydrogen-bond topology governs not only electronic energetics but also mesoscale organization, both of which are essential for efficient charge transport. Table 1 Photoconductivity ( ϕ∑ µ ) values, rate constants ( k , calculated 3 µs after pulse excitation) and half lifetime ( t 1/2 ) values for HDPPBA-2C , HDPPBA-4C and HDPPBA-6C. ϕ∑µ (cm 2 V − 1 s − 1 ) k (s − 1 ) t 1/2 (s) HDPPBA-2C 1.5 × 10 –5 1 × 10 5 5 × 10 − 6 HDPPBA-4C 3.5 × 10 –5 4 × 10 4 2 × 10 − 5 HDPPBA-6C 2.8 × 10 –5 4 × 10 4 2 × 10 − 5 Even though the FP-TRMC measurements give information on charge transport at the nanoscale, these results are very valuable to predict the performance of the different derivatives in lab-scale devices. Solution-processed OFET transistors with a top-contact/bottom-gate structure were fabricated as described below. From the saturation region in the device transfer curves, the field effect mobility (µ), threshold voltage (V T ), and on/off current ratio (I ON /IO FF ) were determined. The electrical parameters of the best-performing devices are summarized in Table 2. Thin films of HDPPH , HDPPBA-2C , HDPPBA-4C and HDPPBA-6C were deposited by drop casting from chloroform solutions (3 mg/ml) onto Si/SiO₂ substrates. After deposition, thermal annealing was carried out at 120°C for 3 hours, to promote molecular organization and improve the film quality. Notably, while HDPPH showed no activity in OFETs, p-type field-effect mobilities of 4 × 10⁻ 6 cm² V⁻¹ s⁻¹, 5 × 10⁻ 3 cm² V⁻¹ s⁻¹ and 2 × 10⁻² cm² V⁻¹ s⁻¹ were obtained for HDPPBA-2C , HDPPBA-4C and HDPPBA-6C , respectively (see output and transfer plots in Fig. 9 ). Thus, the field effect mobilities increase with the elongation of the alkyl spacer between the amide groups and the DPP core. This is probably due to the presence of intermolecular hydrogen-bonds in HDPPBA-4C and HDPPBA-6C , which modifies thin film morphology, as shown in AFM images, thus favouring charge transport. Note also that the participation of the carbonyl group of the DPP unit in the hydrogen-bonds formation, as previously demonstrated by our group, also enhances the π-conjugation, facilitating charge injection and transport. In contrast, in HDPPBA-2C the proximity of the amide group to the conjugated backbone favours intramolecular hydrogen-bonds, which has two effects; i) inhibit the formation of hydrogen-bonded supramolecular aggregates; ii) has a clear impact on the molecular structure since the molecular skeleton losses planarity, decreasing effective conjugation, and thus, decreasing the ability to inject and stabilize charge carriers. These results corroborate that modifying the position of amide groups on side chains is a highly effective strategy for promoting π-conjugation, stabilising charged species and generating supramolecular aggregates. Table 2. OFET electrical data for best-performing deposited films of the indicated semiconductors measured in vacuum. a Substrates treated with OTS and thermal annealed at 120ºC. Conclusions This study demonstrates that hydrogen-bond topology, rather than hydrogen bonding per se, governs conjugation pathways, charge stabilization, and charge transport in DPP-based small-molecule semiconductors. Precise control over the spatial positioning of amide functionalities enables selective promotion of intra- or intermolecular hydrogen-bonding, with important consequences for molecular planarity, supramolecular organization, and electronic coupling in the solid state. Proximal amide groups induce intramolecular hydrogen-bonding that disrupts backbone planarity, restricts effective π-conjugation, and limits the formation of electronically connected domains, leading to higher oxidation onsets, short-lived charge carriers, and poor device performance. In contrast, distal amide placement favours intermolecular hydrogen-bonding involving the DPP carbonyl groups, stabilizing planar conformations, extending conjugation pathways across neighbouring molecules, and generating heterogeneous but electronically delocalized environments capable of stabilizing long-lived charges. These effects are reflected in lowered oxidation energetics, enhanced photoconductivity lifetimes, and significantly improved field-effect mobilities. Taken together, these findings establish hydrogen-bond topology as a powerful and general design principle for engineering the electronic structure and charge-transport properties of supramolecular organic semiconductors. Declarations Conflicts of interest There are no conflicts of interest to declare Author contributions G.M. synthesized and provided the molecules for the study. R.G.-N. fabricated all the devices, performed the electrochemical oxidation experiments, interpreted the results and wrote the manuscript. P.L.G. performed the DFT calculations. K.I.H. performed the electrochemical experiments. W.M. and S.S. fabricated and measured the electrodeless devices, and interpreted the results. A.R.C. and R.P.O. conceived, supervised the work, interpreted the results, and wrote the manuscript. Acknowledgments The work at the University of Málaga was supported by the MICINN (project PID2022-139548GB-I00). R. G.-N. thanks the MICINN for a FPI predoctoral fellowship (PRE2020-092327). A.R.C. and G.M. thank the Graduate School of Complex Systems Chemistry of Strasbourg for his doctoral fellowship funded by the French National Research Agency (CSC-IGSANR-17-EURE-0016). The authors thank the Agence Nationale de la Recherche (ANR JCJC TOTALBOND 2020). R.P.O and A.R.C. acknowledge the MICIIN for the REDES project "RED2022-134503-T". A.R.C. and R. G.-N. thank support from the Spanish Ministry of Science and Innovation and the Spanish State Research Agency (Project ATR2024-154740). The authors would also like to thank the computer resources, technical expertise and assistance provided by the SCBI (Supercomputing and Bioinformatics) centre of the University of Málaga. The Vibrational spectroscopy (EVI) lab of the Research Central Services (SCAI) of the University of Málaga is also gratefully acknowledged. References Głowacki, E. D.; Irimia‐Vladu, M.; Kaltenbrunner, M.; Gsiorowski, J.; White, M. S.; Monkowius, U.; Romanazzi, G.; Suranna, G. P.; Mastrorilli, P.; Sekitani, T.; Bauer, S.; Someya, T.; Torsi, L.; Sariciftci, N. S. Hydrogen-Bonded Semiconducting Pigments for Air-Stable Field-Effect Transistors. Advanced Materials 2013 , 25 (11), 1563–1569. https://doi.org/10.1002/adma.201204039. Huang, C.-H.; McClenaghan, N. D.; Kuhn, A.; Hofstraat, J. W.; Bassani, D. M. Enhanced Photovoltaic Response in Hydrogen-Bonded All-Organic Devices. Organic Letters 2005 , 7 (16), 3409–3412. https://doi.org/10.1021/ol050966l. Głowacki, E. D.; Coskun, H.; Blood-Forsythe, M. 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07:52:21","extension":"html","order_by":22,"title":"","display":"","copyAsset":false,"role":"acdc-reference","size":85568,"visible":true,"origin":"","legend":"","description":"","filename":"earlyproof.html","url":"https://assets-eu.researchsquare.com/files/rs-8657581/v1/8f5d3e1ed6577519b4f9965c.html"},{"id":100949832,"identity":"862d4d45-ee50-42f5-9909-fb57e7f23f5e","added_by":"auto","created_at":"2026-01-23 07:05:58","extension":"jpeg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":406870,"visible":true,"origin":"","legend":"\u003cp\u003ea) Chemical structures of \u003cstrong\u003eHDPPH\u003c/strong\u003e, \u003cstrong\u003eHDPPBA-2C\u003c/strong\u003e, \u003cstrong\u003eHDPPBA-4C\u003c/strong\u003e and \u003cstrong\u003eHDPPBA-6C\u003c/strong\u003e. DFT-computed global minimum energy geometries for b)\u003cstrong\u003e HDPPBA-6C \u003c/strong\u003eand c)\u003cstrong\u003e HDPPBA-2C\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"floatimage1.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8657581/v1/57dcd335f85afa38b26aeaad.jpeg"},{"id":100862191,"identity":"39d8203e-1369-42e9-b214-8e33c4c2629c","added_by":"auto","created_at":"2026-01-22 07:52:20","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":299887,"visible":true,"origin":"","legend":"\u003cp\u003eDFT-calculated molecular energies (B3LYP/6-31G**) for the studied compounds along with topologies of the HOMO and LUMO orbitals (isovalue of 0.035 a.u)\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-8657581/v1/594e437505c8630a643d1945.png"},{"id":100862193,"identity":"57240f8e-4761-41e3-95c2-36b857b98e46","added_by":"auto","created_at":"2026-01-22 07:52:20","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":308073,"visible":true,"origin":"","legend":"\u003cp\u003eUV-Vis spectra in chloroform and thin film prepared by drop casting from the same solvent for a) \u003cstrong\u003eHDPPB\u003c/strong\u003e, b) \u003cstrong\u003eHDPPBA-2C\u003c/strong\u003e, c) \u003cstrong\u003eHDPPBA-4C \u003c/strong\u003eand d) \u003cstrong\u003eHDPPBA-6C\u003c/strong\u003e.\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-8657581/v1/643da27841bc611198f05d52.png"},{"id":100949482,"identity":"86f16552-64d8-4c36-b88b-784e9c01fd85","added_by":"auto","created_at":"2026-01-23 07:03:06","extension":"jpeg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":660421,"visible":true,"origin":"","legend":"\u003cp\u003eIR spectra of \u003cstrong\u003eHDPPBA-2C\u003c/strong\u003e, \u003cstrong\u003eHDPPBA-4C\u003c/strong\u003e,\u003cstrong\u003e HDPPBA-6C\u003c/strong\u003e and\u003cstrong\u003e HDPPH \u003c/strong\u003ein the carbonyl region: a) experimental and b)\u003cstrong\u003e \u003c/strong\u003eB3LYP/6-31G** IR theoretical spectra. IR spectra in the amide region of \u003cstrong\u003eHDPPBA-2C\u003c/strong\u003e, \u003cstrong\u003eHDPPBA-4C \u003c/strong\u003eand \u003cstrong\u003eHDPPBA-6C\u003c/strong\u003e: c) experimental and d)\u003cstrong\u003e \u003c/strong\u003eB3LYP/6-31G** IR theoretical spectra\u003c/p\u003e","description":"","filename":"floatimage4.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8657581/v1/b42d94eead63486ad5613e46.jpeg"},{"id":100950050,"identity":"754d0e47-dd66-4bae-8cea-e9f0565a5830","added_by":"auto","created_at":"2026-01-23 07:06:45","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":160147,"visible":true,"origin":"","legend":"\u003cp\u003ea) Raman spectra (1064 nm) of \u003cstrong\u003eHDDPH\u003c/strong\u003e, \u003cstrong\u003eHDPPBA-2C\u003c/strong\u003e, \u003cstrong\u003eHDPPBA-4C \u003c/strong\u003eand \u003cstrong\u003eHDPPBA-6C\u003c/strong\u003e as bulk samples.\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-8657581/v1/c7a7b7d699321e205d4354c7.png"},{"id":100950262,"identity":"99fa8857-f8af-43e3-8328-883ef9460c21","added_by":"auto","created_at":"2026-01-23 07:07:25","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":39356,"visible":true,"origin":"","legend":"\u003cp\u003eThin film cyclic voltammetry spectra recorded in acetonitrile/TBAPF6 (0.2 M) for \u003cstrong\u003eHDPPH,\u003c/strong\u003e \u003cstrong\u003eHDPPBA-2C\u003c/strong\u003e, \u003cstrong\u003eHDPPBA-4C\u003c/strong\u003e and\u003cstrong\u003e HDPPBA-6C\u003c/strong\u003e.\u003c/p\u003e","description":"","filename":"floatimage6.png","url":"https://assets-eu.researchsquare.com/files/rs-8657581/v1/feca708faa2e2265bfea3168.png"},{"id":100862208,"identity":"6caaa59e-b3f5-46cb-ab4c-d85317346032","added_by":"auto","created_at":"2026-01-22 07:52:21","extension":"jpeg","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":54211,"visible":true,"origin":"","legend":"\u003cp\u003eKinetic traces of photoconductivity transients of \u003cstrong\u003eHDPPBA-2C\u003c/strong\u003e, \u003cstrong\u003eHDPPBA-4C\u003c/strong\u003e and \u003cstrong\u003eHDPPBA-6C\u003c/strong\u003e cast from CHCl\u003csub\u003e3\u003c/sub\u003e.\u003c/p\u003e","description":"","filename":"floatimage7.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8657581/v1/983b566418bca70b31b3072b.jpeg"},{"id":100949471,"identity":"05435b3a-1e74-41d8-ab55-927407201a93","added_by":"auto","created_at":"2026-01-23 07:02:52","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":1030237,"visible":true,"origin":"","legend":"\u003cp\u003eAFM of semiconducting thin films, a) \u003cstrong\u003eHDDPH\u003c/strong\u003e, b) \u003cstrong\u003eHDPPBA-2C\u003c/strong\u003e, c) \u003cstrong\u003eHDPPBA-4C \u003c/strong\u003eand \u0026nbsp;d) \u003cstrong\u003eHDPPBA-6C\u003c/strong\u003e.\u003c/p\u003e","description":"","filename":"floatimage8.png","url":"https://assets-eu.researchsquare.com/files/rs-8657581/v1/23d5403db9e0ead415a8bbee.png"},{"id":100862212,"identity":"13739dd3-2571-41a5-998e-679fd61e5aef","added_by":"auto","created_at":"2026-01-22 07:52:21","extension":"jpeg","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":318705,"visible":true,"origin":"","legend":"\u003cp\u003eTransfer (a-c) and output (d-f) of \u003cstrong\u003eHDPPBA-2C\u003c/strong\u003e, \u003cstrong\u003eHDPPBA-4C \u003c/strong\u003eand \u003cstrong\u003eHDPPBA-6C\u003c/strong\u003e. The transfer characteristics were measured at a constant source–drain voltage of -80 V. The gate voltage in the output plots varies from 0 to -80 V in steps of 10 V.\u003c/p\u003e","description":"","filename":"floatimage9.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8657581/v1/0be83f776a0e25eda8f0a7bc.jpeg"},{"id":101298948,"identity":"ae7d8a71-f6ec-44a1-b077-ccbc47eea417","added_by":"auto","created_at":"2026-01-28 09:38:12","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4399862,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8657581/v1/9c07c6b9-07a7-461a-94a5-97be7c1bd2ba.pdf"},{"id":100862206,"identity":"4553eb03-d51b-4560-97de-04b3aad83b94","added_by":"auto","created_at":"2026-01-22 07:52:21","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":2557891,"visible":true,"origin":"","legend":"","description":"","filename":"SupportingInformation.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8657581/v1/8d8840bd8f2355d4b0fcffc3.pdf"}],"financialInterests":"The authors declare no competing interests.","formattedTitle":"\u003cp\u003e\u003cstrong\u003eModulation of Conjugation Pathways and Charge Transport in Supramolecular Semiconductors via Hydrogen-Bonding Topology\u003c/strong\u003e\u003c/p\u003e","fulltext":[{"header":"Introduction","content":"\u003cp\u003eIn the rapidly evolving field of organic semiconductors, hydrogen-bonded materials have emerged as a class of compounds with promising electronic properties and tuneable functionalities.\u003csup\u003e1\u0026ndash;6\u003c/sup\u003e Within this broad class of materials, small molecules that integrate π-conjugated cores with hydrogen-bonding motifs are of particular interest due to their structural versatility and potential in electronic applications.\u003csup\u003e2,7,8\u003c/sup\u003e In these systems, intra- and intermolecular hydrogen-bonding can significantly influence molecular planarity, effective π-conjugation length, and solid-state organization, all of which are critical parameters governing charge transport.\u003csup\u003e9\u0026ndash;12\u003c/sup\u003e In this sense, a key design challenge lies in modulating hydrogen-bonding patterns to favor extended conjugation pathways that facilitate or block the generation of charge carriers, altering the final electrical performance. In particular, hydrogen-bonding may involve either pendant functional groups or the conjugated backbone itself, potentially altering conjugation pathways by favoring or suppressing specific electronic couplings. Despite its importance, the role of hydrogen-bond topology, that is, whether hydrogen-bonding occurs intra- or intermolecularly and how it engages the π-conjugated core, remains insufficiently understood, especially in small-molecule semiconductors.\u003c/p\u003e \u003cp\u003eA central challenge in the rational design of hydrogen-bonded semiconductors is therefore not merely the introduction of hydrogen-bonding motifs, but the controlled modulation of conjugation pathways through precise molecular design. In this context, intramolecular-hydrogen-bonding may rigidify molecular conformations or, conversely, induce backbone distortion, while intermolecular hydrogen-bonding can promote supramolecular order and electronic delocalization across neighboring molecules. Disentangling these competing effects requires molecular systems in which hydrogen-bonding topology can be systematically tuned without altering the electronic nature of the conjugated core.\u003c/p\u003e \u003cp\u003eDiketopyrrolopyrrole (DPP) derivatives represent an ideal platform to address this challenge. DPP-based small molecules are well known for their strong light absorption, high charge-carrier mobilities, and structural robustness, and their electronic properties are highly sensitive to backbone planarity and intermolecular interactions.\u003csup\u003e13,14\u003c/sup\u003e Recently, hydrogen-bonding has been successfully exploited in DPP-based materials to enhance charge transport, improve air stability, and control self-assembly.\u0026sup3;\u003csup\u003e,\u003c/sup\u003e⁵\u003csup\u003e,\u003c/sup\u003e⁶ Nevertheless, the specific consequences of engaging the DPP carbonyl groups in hydrogen-bonding, particularly in distinguishing intra- versus intermolecular interactions, have only begun to be explored.\u003c/p\u003e \u003cp\u003eIn our recent work, we demonstrated that a thiophene-capped DPP derivative bearing distal amide groups exhibits superior charge-transport properties compared to a non-hydrogen-bonding analogue.\u0026sup1;⁵ Notably, the enhanced performance was attributed not only to supramolecular aggregation, but to a specific intermolecular hydrogen-bond between the DPP carbonyl and a pendant amide of a neighboring molecule. This interaction favored a linear thiophene\u0026ndash;DPP\u0026ndash;thiophene conjugation pathway while suppressing a competing cross-conjugated route involving the DPP carbonyls, highlighting hydrogen-bonding as an effective lever to modulate conjugation pathways.\u003csup\u003e15\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eHere, we build on this concept and investigate how the distance between hydrogen-bonding motifs and the conjugated DPP core governs hydrogen-bond topology, molecular planarity, and electronic properties. To this end, we design and synthesize a series of thiophene-capped DPP small molecules bearing amide functionalities positioned at precisely defined distances from the π-conjugated backbone, namely \u003cb\u003eHDPPBA-2C\u003c/b\u003e, \u003cb\u003eHPDDBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea). This molecular design allows selective promotion of either intramolecular or intermolecular hydrogen-bonding while preserving the electronic identity of the conjugated core. For comparison, we have included as well a control molecule, \u003cb\u003eHDPPBA\u003c/b\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea) unable to form hydrogen-bonds, that was previously synthesized and reported by us.\u003csup\u003e16\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eThrough a combined experimental and theoretical approach, including density functional theory calculations (DFT), UV\u0026ndash;vis and vibrational spectroscopies, electrochemistry, electrodeless photoconductivity measurements, atomic force microscopy, and organic field-effect transistor (OFET) characterization, we demonstrate that hydrogen-bond topology plays a decisive role in the modulation of conjugation pathways and charge transport. Intriguingly, we observe deviations from previously reported conjugation mechanisms, finding a new role for intramolecular hydrogen-bonding in shaping the electronic landscape of these materials. Proximal amide groups favor intramolecular hydrogen-bonding that disrupts backbone planarity and limits effective π-conjugation, whereas distal amide placement promotes intermolecular hydrogen-bonding, enhanced supramolecular organization, and improved charge transport. Although this study focuses on DPP-based semiconductors, the underlying design principle, specifically the modulation of conjugation pathways through controlled hydrogen-bond topology, is broadly applicable to other hydrogen-bonded π-conjugated small molecules and supramolecular semiconductors.\u003c/p\u003e \u003cp\u003eTogether, our results hold significance for the development of efficient organic semiconductor materials but also contribute to the broader understanding of the role of hydrogen-bonding in shaping the electronic properties of functional molecular systems, even those based on particularly small molecules. Ultimately, these findings aim to provide valuable insights that can guide the rational design of hydrogen-bonded semiconductors, opening new avenues for the progress of organic optoelectronics.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"Results and discussion","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003eSynthesis\u003c/h2\u003e \u003cp\u003eCompounds \u003cb\u003e1\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e were synthesized following a protocol previously reported by our group.\u003csup\u003e16\u003c/sup\u003e On the other hand, \u003cb\u003eHDPPBA-2C\u003c/b\u003e and \u003cb\u003eHDPPBA-4C\u003c/b\u003e were obtained starting from derivative \u003cb\u003e1\u003c/b\u003e, and introducing the hydrogen-bonding motifs in subsequent steps (Scheme S1).\u003csup\u003e16\u003c/sup\u003e Initially, product \u003cb\u003e1\u003c/b\u003e was alkylated using \u003cem\u003et\u003c/em\u003e-butyl bromoacetate and \u003cem\u003et\u003c/em\u003e-butyl 4-bromobutanoate to afford \u003cb\u003eHDPP-2C-P\u003c/b\u003e and \u003cb\u003eHDPP-4C-P\u003c/b\u003e in 17% and 13% yield, respectively.\u003csup\u003e17\u003c/sup\u003e The low yields are attributed to the reduced solubility of the starting material \u003cb\u003e1\u003c/b\u003e in acetone, in addition to the expected formation of \u003cem\u003eN,O\u003c/em\u003e- and/or \u003cem\u003eO,O\u0026rsquo;\u003c/em\u003e- alkylated isomers as byproducts.\u003csup\u003e18\u003c/sup\u003e Then, a deprotection step was performed using trifluoroacetic acid (TFA) to isolate \u003cb\u003eHDPP-2C-acid\u003c/b\u003e and \u003cb\u003eHDPP-4C-acid\u003c/b\u003e with 78% and 89% yield, respectively. Finally, the resulting diacids were functionalized with 1-decanamine and 1-octanamine through a peptide coupling reaction using hexafluorophosphate benzotriazole tetramethyl uronium (HBTU)\u003csup\u003e19\u003c/sup\u003e to obtain \u003cb\u003eHDPPBA-2C\u003c/b\u003e and \u003cb\u003eHDPPBA-4C\u003c/b\u003e in 79 and 89% yields, respectively (Scheme S1). The final molecules were characterized by \u003csup\u003e1\u003c/sup\u003eH, \u003csup\u003e13\u003c/sup\u003eC-NMR and high-resolution mass spectrometry (see SI for detailed description and full characterization).\u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003eStructural and optical properties\u003c/h3\u003e\n\u003cp\u003eTo elucidate how hydrogen-bond topology influences molecular structure and effective π-conjugation, ground-state density functional theory (DFT) calculations were performed on the amide-functionalized DPP derivatives. The optimized geometries reveal a pronounced dependence of backbone planarity on the relative position of the amide groups with respect to the conjugated core\u003c/p\u003e \u003cp\u003e \u003cb\u003eHDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e adopt nearly fully planar conformations, with dihedral angles close to 0\u0026deg; between the DPP core and the flanking thiophene units (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb). This planarity is stabilized by weak intramolecular O\u0026ndash;H interactions between the DPP carbonyl oxygen and the adjacent thiophene hydrogen atoms, which effectively lock the thiophene\u0026ndash;DPP\u0026ndash;thiophene backbone in a coplanar geometry (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb and Figure S1 for \u003cb\u003eHDPPBA-4C\u003c/b\u003e). The calculated O-H distance is 2.1 \u0026Aring;, lower than the sum of the Van der Waals radii (2.72 \u0026Aring;), corroborating the aforementioned interactions. In contrast, \u003cb\u003eHDPPBA-2C\u003c/b\u003e exhibits a significantly distorted backbone, with dihedral angles of approximately 15\u0026deg; between the DPP and thiophene units. In this case, the proximity of the amide groups enables the formation of intramolecular hydrogen-bonds between the amide N\u0026ndash;H and the DPP carbonyl oxygen, suppressing the stabilizing O\u0026ndash;H interactions observed in the longer-spacer derivatives and inducing backbone twisting (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ec). These structural differences have direct consequences for the electronic structure. The energies and topologies of the studied compounds were also predicted (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e and Figure S2). As expected, the frontier molecular orbitals in the three studied molecules are delocalized over the whole conjugated skeleton with a greater contribution on the DPP core. DFT calculations point out quite similar Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) energy levels for \u003cb\u003eHDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e, with energy gaps of 2.41\u0026ndash;2.42 eV, very similar to those of the control \u003cb\u003eHDPPH\u003c/b\u003e. On the contrary, in \u003cb\u003eHDPPBA-2C\u003c/b\u003e, both HOMO and LUMO energy levels are stabilized with respect to those of \u003cb\u003eHDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e, in around 0.3\u0026ndash;0.41 eV in the case of the LUMO level and 0.36\u0026ndash;0.46 for the HOMO level. Thus, the theoretical energy gap is slightly enlarged, being 2.47 eV for \u003cb\u003eHDPPBA-2C\u003c/b\u003e. This is ascribed to the planarity loss due to the hydrogen-bond intramolecular interactions.\u003c/p\u003e \u003cp\u003eTogether, the DFT results establish that hydrogen-bond topology controls molecular planarity and π-conjugation, providing a structural basis for the distinct electronic and transport properties observed experimentally.\u003c/p\u003e \u003cp\u003eThe influence of hydrogen-bond topology on the optical properties of the DPP derivatives was investigated by UV\u0026ndash;vis absorption spectroscopy in solution and in thin films (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). The results were rationalized with the help of the time-dependent density functional theory (TD-DFT) (Figure S3). In dilute chloroform solutions, all three derivatives as well as the control molecule exhibit similar absorption spectra, characterized by two intense bands typical of DPP chromophores, having absorption maxima around λ\u0026thinsp;=\u0026thinsp;520 nm and λ\u0026thinsp;=\u0026thinsp;560 nm (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea-d, black traces). Although the overall spectra are similar across the series, \u003cb\u003eHDPPBA-2C\u003c/b\u003e shows a slight blue-shift of the absorption maxima compared to \u003cb\u003eHDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e. This subtle difference is consistent with reduced backbone planarity and shorter effective conjugation length in \u003cb\u003eHDPPBA-2C\u003c/b\u003e, in agreement with DFT predictions. The lowest-energy absorption, assigned to a single electron HOMO\u0026rarr;LUMO transition,\u003csup\u003e20\u003c/sup\u003e appears at comparable wavelengths for the three compounds, reflecting the limited extent of hydrogen-bonding under these conditions due to good solubility and low aggregation.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIn thin films (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea-d, red traces), the absorption spectra broaden and red-shift relative to solution, with main bands around 490 and 610 nm, indicating enhanced intermolecular interactions and solid-state organization. However, despite the resemblance between the spectra of the three studied molecules, UV-Vis absorption spectra already account for the skeleton planarity loss in \u003cb\u003eHDPPBA-2C\u003c/b\u003e, since both solution and film UV-Vis maxima are slightly blue-shifted respect those of \u003cb\u003eHDPPH, HDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e. These results indicate that differences in hydrogen-bond topology primarily manifest in the solid state, where molecular packing and supramolecular organization amplify their electronic consequences.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e\n\u003ch3\u003eVibrational Spectroscopic analysis\u003c/h3\u003e\n\u003cp\u003eVibrational spectroscopy was employed to experimentally identify hydrogen-bond formation and assess its impact on molecular conjugation in the solid state. Attenuated total reflectance infrared (ATR-IR) spectra of the stretching vibration of the C\u0026thinsp;=\u0026thinsp;O group (ν(C\u0026thinsp;=\u0026thinsp;O)), reveal two distinct C\u0026thinsp;=\u0026thinsp;O stretching contributions for the amide-functionalized derivatives, corresponding to the carbonyl group in the DPP core and the pendant amide groups (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea, see the eigenvectors in Figure S4). \u003cb\u003eHDPPH\u003c/b\u003e displays a unique IR band at 1656 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea), helping us to identify the ν(C\u0026thinsp;=\u0026thinsp;O) of the DPP core in the \u003cb\u003eHDPPBA\u003c/b\u003e derivatives. Therefore, the DPP ν (C\u0026thinsp;=\u0026thinsp;O) IR band is recorded at 1653 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, 1659 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1657 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for \u003cb\u003eHDPPBA-2C\u003c/b\u003e, \u003cb\u003eHDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e, respectively (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea). While the DPP carbonyl stretching frequency remains nearly invariant across the series, with a subtle downshift found in \u003cb\u003eHDPPBA-2C\u003c/b\u003e, the amide C\u0026thinsp;=\u0026thinsp;O vibration exhibits a pronounced downshift for \u003cb\u003eHDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e (1642 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) relative to \u003cb\u003eHDPPBA-2C\u003c/b\u003e (1670 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e). This downshift is indicative of strong hydrogen-bond engagement of the amide carbonyls in the longer-spacer derivatives, consistent with intermolecular hydrogen-bonding. In contrast, the higher-frequency amide C\u0026thinsp;=\u0026thinsp;O stretching observed for \u003cb\u003eHDPPBA-2C\u003c/b\u003e suggests the absence of strong intermolecular interactions involving the amide group. Theoretical DFT calculations (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb and Figure S5) predict this IR band at around 1710 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, which is consistent with the position found for \u003cb\u003eHDPPBA-2C\u003c/b\u003e. Thus, ATR-IR data points out to the formation of hydrogen-bonding interactions in \u003cb\u003eHDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e, due to the enlargement of the C\u0026thinsp;=\u0026thinsp;O bond of the amide group.\u003c/p\u003e \u003cp\u003eAnalysis of the N\u0026ndash;H stretching region further supports this assignment (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ec and \u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed). Experimental spectra show hydrogen-bonded N\u0026ndash;H vibrations for all three compounds. However, DFT calculations (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed) predict significant N\u0026ndash;H red-shifting only for \u003cb\u003eHDPPBA-2C\u003c/b\u003e (3381 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), consistent with intramolecular hydrogen-bonding that can be captured at the single-molecule level (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed), while for \u003cb\u003eHDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e that IR vibration is predicted at much higher wavenumbers (\u0026sim;3500 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), characteristic of free amides (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed). These results indicate that the three compounds are involved in hydrogen-bonding interactions but of different nature. Thus, \u003cb\u003eHDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e form intermolecular hydrogen-bonding interactions, while the nature of such interactions in \u003cb\u003eHDPPBA-2C\u003c/b\u003e is of intramolecular character, between the N-H group of the amide unit and the C\u0026thinsp;=\u0026thinsp;O group of the DPP unit, since theoretical calculations of a single molecule in vacuum are able to predict the interaction. The different nature of the hydrogen-bonds in \u003cb\u003eHDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e versus \u003cb\u003eHDPPBA-2C\u003c/b\u003e also explains the subtle downshift of the ν (C\u0026thinsp;=\u0026thinsp;O) vibration of the DPP group in the latter, which is, in that case, involved in the intramolecular interaction and the upshift of the ν (C\u0026thinsp;=\u0026thinsp;O) vibration of the amide, being free of interaction (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eComplementary insight into conjugation is provided by Raman spectroscopy, which probes the collective ν (C\u0026thinsp;=\u0026thinsp;C/C-C) vibration along the thiophene\u0026ndash;DPP\u0026ndash;thiophene backbone (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e, see eigenvectors in Figure S6 and theoretical calculated spectra in Figure S7). This Raman vibration is recorded at 1528 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for \u003cb\u003eHDPPH\u003c/b\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e), while it is slightly upshifted (1534 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) for \u003cb\u003eHDPPBA-2C\u003c/b\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e), which is an indicative of the loss of planarity due to the formation of intramolecular hydrogen-bond interactions, as seen above. On the contrary, the position of this Raman band in \u003cb\u003eHDPPBA-6C\u003c/b\u003e, \u003cb\u003eHDPPBA-4C\u003c/b\u003e, where intermolecular hydrogen-bonds are present, is comparable to that of the control molecule (1528 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) but with a clear widening (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e). Thus, two different contributions at 1526\u0026ndash;1527 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1530 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e are found, indicative of the coexistence of various conjugation paths. This has been previously analyzed by our group\u003csup\u003e15\u003c/sup\u003e and is ascribed to some participation of the carbonyl group of the DPP unit in the supramolecular hydrogen-bond interactions, favoring π-conjugation extension. Overall, vibrational spectroscopy corroborates the DFT results and demonstrates that hydrogen-bond topology governs both backbone planarity and effective conjugation in the solid state.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e\n\u003ch3\u003eElectrochemical study\u003c/h3\u003e\n\u003cp\u003eCyclic voltammetry measurements in solution (1 mM in CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e) reveal similar redox behaviour for all three derivatives, with two one-electron oxidation processes and two reduction process observed within comparable potential windows (Figure S8 and Table S1). The HOMO and LUMO energy levels were calculated from the oxidation and reduction onset potentials, respectively and using ferrocene as a reference (Table S1). The HOMO levels of \u003cb\u003eHDPPH\u003c/b\u003e, \u003cb\u003eHDPPBA-2C\u003c/b\u003e, \u003cb\u003eHDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e were calculated to be -5.1, -5.14, -5.1 and \u0026minus;\u0026thinsp;5.09 eV, correspondingly. The modest shifts in oxidation potentials, with \u003cb\u003eHDPPBA-2C\u003c/b\u003e displaying slightly higher values, are consistent with its reduced backbone planarity and stabilized frontier orbitals predicted by DFT. On the other hand, the obtained LUMO values were \u0026minus;\u0026thinsp;3.37, -3.39, -3.34 and \u0026minus;\u0026thinsp;3.37 eV (See SI for details on the HOMO and LUMO calculations). The four derivatives have similar band gaps, being 1.73 eV, 1.75 eV, 1.76 eV and 1.72 eV for \u003cb\u003eHDPPBA-2C\u003c/b\u003e, \u003cb\u003eHDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e, respectively. Importantly, the overall similarity of the solution-phase electrochemistry indicates that the intrinsic redox properties of the isolated molecules are largely unaffected by the position of the amide groups under these conditions, where hydrogen-bonding and aggregation are negligible.\u003c/p\u003e \u003cp\u003eCV experiments in thin films drop cast from CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e solutions were performed using acetonitrile to dissolve TBAPF\u003csup\u003e6\u003c/sup\u003e as the supporting electrolyte (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e, Figure S9 and Table S2). Cyclic voltammetry performed on drop-cast thin films reveals marked differences in the electrochemical response as a function of hydrogen-bond topology. While all derivatives exhibit oxidation features characteristic of DPP-based semiconductors, the voltammograms of \u003cb\u003eHDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e display broader oxidation waves with partially overlapping oxidation bands compared to \u003cb\u003eHDPPBA-2C\u003c/b\u003e. This behaviour is indicative of a larger population of electroactive sites and enhanced charge delocalization in the solid state. In contrast, \u003cb\u003eHDPPBA-2C\u003c/b\u003e shows comparatively sharper and less intense redox features, consistent with a more localized oxidation process. The HOMO levels of \u003cb\u003eHDPPH\u003c/b\u003e, \u003cb\u003eHDPPBA-2C\u003c/b\u003e, \u003cb\u003eHDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e were calculated to be -5.63, -5.57, -5.48 and \u0026minus;\u0026thinsp;5.56 eV, correspondingly. The obtained LUMO values were \u0026minus;\u0026thinsp;3.74, -3.88, -3.83 and \u0026minus;\u0026thinsp;3.87 eV for \u003cb\u003eHDPPH\u003c/b\u003e, \u003cb\u003eHDPPBA-2C\u003c/b\u003e, \u003cb\u003eHDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e, respectively. The energy band gaps for the hydrogen-bonded derivatives are similar, ranging from 1.66 eV for \u003cb\u003eHDPPBA-4C\u003c/b\u003e to 1.69 eV for \u003cb\u003eHDPPBA-2C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e. Despite the similar energy band gaps, the positioning of the HOMO levels shows slightly higher energy for \u003cb\u003eHDPPBA-2C\u003c/b\u003e as a result of the loss of planarity and more difficult oxidation. These trends agree with our previous findings on thiophene-capped DPP derivatives, where intermolecular hydrogen-bonding involving the DPP carbonyl groups was shown to promote extended conjugation pathways and stabilize charged species in the solid state.\u003csup\u003e15\u003c/sup\u003e In the present series, the distal positioning of the amide groups in \u003cb\u003eHDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e favours intermolecular hydrogen-bond formation, facilitating electronic communication between neighbouring molecules and leading to electrochemically stabilized oxidized states. Conversely, the predominance of intramolecular hydrogen-bonding in \u003cb\u003eHDPPBA-2C\u003c/b\u003e disrupts backbone planarity and limits intermolecular electronic coupling.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cb\u003eAnalysis of electronic properties by spectroelectrochemistry. Charge carriers\u0026rsquo; stabilization.\u003c/b\u003e \u003c/p\u003e \u003cp\u003eIn order to evaluate the ability of the studied semiconductors to stabilize charge carriers and to probe if the differences in hydrogen-bonding topology plays a role in the formation of charged species, we performed \u003cem\u003ein situ\u003c/em\u003e spectroelectrochemical studies in dilute dichloromethane solution (10\u003csup\u003e-4\u003c/sup\u003eM) at room temperature using 0.1M Bu\u003csub\u003e4\u003c/sub\u003eNPF\u003csub\u003e6\u003c/sub\u003e as supporting electrolyte and an optically transparent thin-layer electrochemical (OTTLE) cell, as well as TD-DFT calculations to support the experimental results. As shown in Figures S10-S13, \u003cb\u003eHDPPBA-2C\u003c/b\u003e, \u003cb\u003eHDPPBA-4C\u003c/b\u003e, \u003cb\u003eHDPPBA-6C\u003c/b\u003e as well as the control \u003cb\u003eHDPPH\u003c/b\u003e behave similarly in solution and able to stabilize one positive charge. The similar behaviour is expected due to the absence or minimization of intermolecular interactions in dilute solutions. Nevertheless, the distortion of the conjugated skeleton of \u003cb\u003eHDPPBA-2C\u003c/b\u003e due to the formation of intramolecular hydrogen-bonds, results in much higher potentials needed to stabilize the charges (Figures S10 to S13).\u003c/p\u003e\n\u003ch3\u003eElectrical studies\u003c/h3\u003e\n\u003cp\u003eTo directly probe charge-carrier dynamics in the solid state, electrodeless photoconductivity measurements were performed using Flash-Photolysis Time-Resolved Microwave Conductivity (FP-TRMC)\u003csup\u003e21,22\u003c/sup\u003e on thin films of the three hydrogen-bonded derivatives prepared by drop casting CHCl\u003csub\u003e3\u003c/sub\u003e solutions of the DPP derivatives. This technique provides a measure of photoconductivity as ΦΣ\u003cem\u003e\u0026micro;\u003c/em\u003e, where Φ is the charge carrier generation quantum yield and Σ\u003cem\u003e\u0026micro;\u003c/em\u003e is the sum of charge carrier mobilities of electrons and holes (See the SI for the measurement details). The thin films are irradiated with a pulsed laser generating charge carriers, being possible to follow their lifetimes before recombination. The kinetic traces of conductivity transients are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e, and the calculated values of photoconductivity (ϕΣ\u003cem\u003e\u0026micro;\u003c/em\u003e), rate constants (\u003cem\u003ek\u003c/em\u003e, calculated 3 \u0026micro;s after pulse excitation) and half lifetime (\u003cem\u003et\u003c/em\u003e\u003csub\u003e1/2\u003c/sub\u003e) are summarized in Table \u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. All compounds exhibit measurable photoconductivity, ranging from 1.5 to 3.5 x 10\u003csup\u003e\u0026minus;\u0026thinsp;5\u003c/sup\u003e cm\u003csup\u003e2\u003c/sup\u003e V\u003csup\u003e\u0026ndash;1\u003c/sup\u003e s\u003csup\u003e\u0026ndash;1\u003c/sup\u003e (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e), being \u003cb\u003eHDPPBA-2C\u003c/b\u003e the derivative with the lowest photoconductivity value. Interestingly, remarkable differences emerge in charge-carrier lifetimes. \u003cb\u003eHDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e display significantly longer carrier lifetimes up to one order of magnitude higher than \u003cb\u003eHDPPBA-2C\u003c/b\u003e, which has charge carrier lifetime values in the same order as \u003cb\u003eHDPPH\u003c/b\u003e unable to form hydrogen-bonds.\u003csup\u003e16\u003c/sup\u003e This indicates that while charge generation efficiencies are similar, charge stabilization and transport are markedly less effective in \u003cb\u003eHDPPBA-2C\u003c/b\u003e.\u003c/p\u003e \u003cp\u003eThis trend mirrors the thin-film CV results. In \u003cb\u003eHDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e, the presence of hydrogen-bond-stabilized electroactive populations facilitates not only charge formation but also charge persistence, consistent with delocalized conjugation pathways and interconnected supramolecular networks. In contrast, the uniform but intramolecularly hydrogen-bonded environment of \u003cb\u003eHDPPBA-2C\u003c/b\u003e enables oxidation but fails to support long-lived, mobile charge carriers.\u003c/p\u003e \u003cp\u003eAtomic force microscopy provides a structural basis for these observations (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e). \u003cb\u003eHDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e form dense, interconnected fibrillar networks, providing continuous pathways for charge transport. In contrast, \u003cb\u003eHDPPBA-2C\u003c/b\u003e self-assembles into shorter, poorly connected domains, which act as barriers to long-range charge migration and promote rapid recombination. Thus, FP-TRMC and AFM together demonstrate that hydrogen-bond topology governs not only electronic energetics but also mesoscale organization, both of which are essential for efficient charge transport.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003ePhotoconductivity (\u003cb\u003eϕ\u0026sum;\u003c/b\u003e\u003cem\u003e\u0026micro;\u003c/em\u003e) values, rate constants (\u003cem\u003ek\u003c/em\u003e, calculated 3 \u0026micro;s after pulse excitation) and half lifetime (\u003cem\u003et\u003c/em\u003e\u003csub\u003e1/2\u003c/sub\u003e) values for \u003cb\u003eHDPPBA-2C\u003c/b\u003e, \u003cb\u003eHDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C.\u003c/b\u003e\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"4\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\"\u0026times;\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\"\u0026times;\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\"\u0026times;\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eϕ\u0026sum;\u0026micro;\u003c/em\u003e (cm\u003csup\u003e2\u003c/sup\u003eV\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003es\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003ek (s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003et\u003csub\u003e1/2\u003c/sub\u003e (s)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eHDPPBA-2C\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026times;\" colname=\"c2\"\u003e \u003cp\u003e1.5 \u0026times; 10\u003csup\u003e\u0026ndash;5\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026times;\" colname=\"c3\"\u003e \u003cp\u003e1 \u0026times; 10\u003csup\u003e5\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026times;\" colname=\"c4\"\u003e \u003cp\u003e5 \u0026times; 10\u003csup\u003e\u0026minus;\u0026thinsp;6\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eHDPPBA-4C\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026times;\" colname=\"c2\"\u003e \u003cp\u003e3.5 \u0026times; 10\u003csup\u003e\u0026ndash;5\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026times;\" colname=\"c3\"\u003e \u003cp\u003e4 \u0026times; 10\u003csup\u003e4\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026times;\" colname=\"c4\"\u003e \u003cp\u003e2 \u0026times; 10\u003csup\u003e\u0026minus;\u0026thinsp;5\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eHDPPBA-6C\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026times;\" colname=\"c2\"\u003e \u003cp\u003e2.8 \u0026times; 10\u003csup\u003e\u0026ndash;5\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026times;\" colname=\"c3\"\u003e \u003cp\u003e4 \u0026times; 10\u003csup\u003e4\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026times;\" colname=\"c4\"\u003e \u003cp\u003e2 \u0026times; 10\u003csup\u003e\u0026minus;\u0026thinsp;5\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eEven though the FP-TRMC measurements give information on charge transport at the nanoscale, these results are very valuable to predict the performance of the different derivatives in lab-scale devices.\u003c/p\u003e \u003cp\u003eSolution-processed OFET transistors with a top-contact/bottom-gate structure were fabricated as described below. From the saturation region in the device transfer curves, the field effect mobility (\u0026micro;), threshold voltage (V\u003csub\u003eT\u003c/sub\u003e), and on/off current ratio (I\u003csub\u003eON\u003c/sub\u003e/IO\u003csub\u003eFF\u003c/sub\u003e) were determined. The electrical parameters of the best-performing devices are summarized in Table\u0026nbsp;2. Thin films of \u003cb\u003eHDPPH\u003c/b\u003e, \u003cb\u003eHDPPBA-2C\u003c/b\u003e, \u003cb\u003eHDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e were deposited by drop casting from chloroform solutions (3 mg/ml) onto Si/SiO₂ substrates. After deposition, thermal annealing was carried out at 120\u0026deg;C for 3 hours, to promote molecular organization and improve the film quality. Notably, while \u003cb\u003eHDPPH\u003c/b\u003e showed no activity in OFETs, p-type field-effect mobilities of 4 \u0026times; 10⁻\u003csup\u003e6\u003c/sup\u003e cm\u0026sup2; V⁻\u0026sup1; s⁻\u0026sup1;, 5 \u0026times; 10⁻\u003csup\u003e3\u003c/sup\u003e cm\u0026sup2; V⁻\u0026sup1; s⁻\u0026sup1; and 2 \u0026times; 10⁻\u0026sup2; cm\u0026sup2; V⁻\u0026sup1; s⁻\u0026sup1; were obtained for \u003cb\u003eHDPPBA-2C\u003c/b\u003e, \u003cb\u003eHDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e, respectively (see output and transfer plots in Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e). Thus, the field effect mobilities increase with the elongation of the alkyl spacer between the amide groups and the DPP core. This is probably due to the presence of intermolecular hydrogen-bonds in \u003cb\u003eHDPPBA-4C\u003c/b\u003e and \u003cb\u003eHDPPBA-6C\u003c/b\u003e, which modifies thin film morphology, as shown in AFM images, thus favouring charge transport. Note also that the participation of the carbonyl group of the DPP unit in the hydrogen-bonds formation, as previously demonstrated by our group, also enhances the π-conjugation, facilitating charge injection and transport. In contrast, in \u003cb\u003eHDPPBA-2C\u003c/b\u003e the proximity of the amide group to the conjugated backbone favours intramolecular hydrogen-bonds, which has two effects; i) inhibit the formation of hydrogen-bonded supramolecular aggregates; ii) has a clear impact on the molecular structure since the molecular skeleton losses planarity, decreasing effective conjugation, and thus, decreasing the ability to inject and stabilize charge carriers. These results corroborate that modifying the position of amide groups on side chains is a highly effective strategy for promoting π-conjugation, stabilising charged species and generating supramolecular aggregates.\u003c/p\u003e \u003cp\u003e \u003cb\u003eTable\u0026nbsp;2.\u003c/b\u003e OFET electrical data for best-performing deposited films of the indicated semiconductors measured in vacuum. \u003csup\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sup\u003eSubstrates treated with OTS and thermal annealed at 120\u0026ordm;C.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e\u003cp\u003e\u003cimg 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\" width=\"598\" height=\"321\"\u003e\u003c/p\u003e"},{"header":"Conclusions","content":"\u003cp\u003eThis study demonstrates that hydrogen-bond topology, rather than hydrogen bonding per se, governs conjugation pathways, charge stabilization, and charge transport in DPP-based small-molecule semiconductors. Precise control over the spatial positioning of amide functionalities enables selective promotion of intra- or intermolecular hydrogen-bonding, with important consequences for molecular planarity, supramolecular organization, and electronic coupling in the solid state. Proximal amide groups induce intramolecular hydrogen-bonding that disrupts backbone planarity, restricts effective π-conjugation, and limits the formation of electronically connected domains, leading to higher oxidation onsets, short-lived charge carriers, and poor device performance. In contrast, distal amide placement favours intermolecular hydrogen-bonding involving the DPP carbonyl groups, stabilizing planar conformations, extending conjugation pathways across neighbouring molecules, and generating heterogeneous but electronically delocalized environments capable of stabilizing long-lived charges. These effects are reflected in lowered oxidation energetics, enhanced photoconductivity lifetimes, and significantly improved field-effect mobilities. Taken together, these findings establish hydrogen-bond topology as a powerful and general design principle for engineering the electronic structure and charge-transport properties of supramolecular organic semiconductors.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e \u003ch2\u003eConflicts of interest\u003c/h2\u003e \u003cp\u003eThere are no conflicts of interest to declare\u003c/p\u003e \u003c/p\u003e\u003ch2\u003eAuthor contributions\u003c/h2\u003e \u003cp\u003eG.M. synthesized and provided the molecules for the study. R.G.-N. fabricated all the devices, performed the electrochemical oxidation experiments, interpreted the results and wrote the manuscript. P.L.G. performed the DFT calculations. K.I.H. performed the electrochemical experiments. W.M. and S.S. fabricated and measured the electrodeless devices, and interpreted the results. A.R.C. and R.P.O. conceived, supervised the work, interpreted the results, and wrote the manuscript.\u003c/p\u003e\u003ch2\u003eAcknowledgments\u003c/h2\u003e \u003cp\u003eThe work at the University of M\u0026aacute;laga was supported by the MICINN (project PID2022-139548GB-I00). R. G.-N. thanks the MICINN for a FPI predoctoral fellowship (PRE2020-092327). A.R.C. and G.M. thank the Graduate School of Complex Systems Chemistry of Strasbourg for his doctoral fellowship funded by the French National Research Agency (CSC-IGSANR-17-EURE-0016). The authors thank the Agence Nationale de la Recherche (ANR JCJC TOTALBOND 2020). R.P.O and A.R.C. acknowledge the MICIIN for the REDES project \"RED2022-134503-T\". A.R.C. and R. G.-N. thank support from the Spanish Ministry of Science and Innovation and the Spanish State Research Agency (Project ATR2024-154740).\u003c/p\u003e \u003cp\u003eThe authors would also like to thank the computer resources, technical expertise and assistance provided by the SCBI (Supercomputing and Bioinformatics) centre of the University of M\u0026aacute;laga. The Vibrational spectroscopy (EVI) lab of the Research Central Services (SCAI) of the University of M\u0026aacute;laga is also gratefully acknowledged.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eGłowacki, E. D.; Irimia‐Vladu, M.; Kaltenbrunner, M.; Gsiorowski, J.; White, M. S.; Monkowius, U.; Romanazzi, G.; Suranna, G. P.; Mastrorilli, P.; Sekitani, T.; Bauer, S.; Someya, T.; Torsi, L.; Sariciftci, N. S. 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Mater.\u003c/em\u003e \u003cstrong\u003e2023\u003c/strong\u003e, \u003cem\u003e5\u003c/em\u003e (9), 5093\u0026ndash;5102. https://doi.org/10.1021/acsaelm.3c00845.\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[{"identity":"2efdfa6d-b1be-406f-b76e-12cb3711386c","identifier":"10.13039/501100011033","name":"Agencia Estatal de Investigación","awardNumber":"ATR2024-154740","order_by":0},{"identity":"f04b1611-544e-4155-9d55-ccba891bab1a","identifier":"10.13039/501100011033","name":"Agencia Estatal de Investigación","awardNumber":"PID2022-139548GB-I00","order_by":1},{"identity":"8bfa9977-be7a-4ece-8b72-6b81c64f1db3","identifier":"10.13039/501100001665","name":"Agence Nationale de la Recherche","awardNumber":"ANR JCJC TOTALBOND 2020","order_by":2},{"identity":"8e3c459e-3660-4d7f-a4bc-350b3806af7c","identifier":"10.13039/501100001665","name":"Agence Nationale de la Recherche","awardNumber":"CSC-IGSANR-17-EURE-0016","order_by":3}],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"highlight":"","institution":"University of Malaga","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Hydrogen-bonding, conjugation modulation, organic semiconductors, supramolecular assembly, charge transport","lastPublishedDoi":"10.21203/rs.3.rs-8657581/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8657581/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003ePrecise control over conjugation pathways is essential for the development of high-performance organic semiconductors, particularly in hydrogen-bonded systems where subtle structural variations can strongly influence molecular planarity, supramolecular organization, and charge transport. Here, we demonstrate that the relative positioning of hydrogen-bonding motifs with respect to a π-conjugated core enables the modulation of conjugation pathways through controlled intra- or intermolecular hydrogen-bonding. A series of thiophene-capped diketopyrrolopyrrole (DPP) small molecules bearing amide functionalities at well-defined distances from the conjugated backbone was designed to selectively favor distinct hydrogen-bonding topologies.\u003c/p\u003e \u003cp\u003eA combined experimental and theoretical approach, including density functional theory calculations, vibrational and electronic spectroscopies, electrochemistry, and solid-state characterization, reveals that proximal amide groups favor intramolecular hydrogen-bonding that disrupts backbone planarity and limits effective π-conjugation. In contrast, distal amide placement promotes intermolecular hydrogen-bonding involving the DPP carbonyl groups, leading to extended conjugation pathways and enhanced supramolecular organization in the solid state. This modulation of hydrogen-bond topology results in markedly different charge-carrier dynamics and transport characteristics, as evidenced by electrodeless photoconductivity measurements and organic field-effect transistor devices.\u003c/p\u003e \u003cp\u003eOverall, this work establishes hydrogen-bond topology, rather than hydrogen-bonding alone, as a key molecular design parameter for the modulation of conjugation extension and charge transport in hydrogen-bonded small-molecule semiconductors, providing general insights for the rational design of functional supramolecular electronic materials.\u003c/p\u003e","manuscriptTitle":"Modulation of Conjugation Pathways and Charge Transport in Supramolecular Semiconductors via Hydrogen-Bonding Topology","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-01-22 07:52:15","doi":"10.21203/rs.3.rs-8657581/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"7beb3139-7f35-4741-8121-e1570b97908b","owner":[],"postedDate":"January 22nd, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":61493727,"name":"Organic Chemistry"},{"id":61493728,"name":"Materials Chemistry"},{"id":61493729,"name":"Electronic Materials and Devices"}],"tags":[],"updatedAt":"2026-01-22T07:52:16+00:00","versionOfRecord":[],"versionCreatedAt":"2026-01-22 07:52:15","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-8657581","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8657581","identity":"rs-8657581","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}