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The poor operational stability of non-fullerene electron acceptor (NFA) organic solar cells (OSCs) currently limits their commercial application. While previous studies have primarily focused on the degradation of the NFA component, we also consider here the electron donor material. We examine the stability of three representative donor polymers, PM6, D18, and PTQ10, paired with the benchmark NFA, Y6. After light soaking PM6 and D18 in air, we find an enhanced conversion of singlet excitons into trapped interchain polaron pairs on sub-100 femtosecond timescales. This process outcompetes electron transfer to Y6, significantly reducing the charge generation yield. However, this pathway is absent in PTQ10. We identify twisting in the benzo[1,2-b:4,5-b′]dithiophene (BDT)-thiophene motif shared by PM6 and D18 as the cause. By contrast, PTQ10 does not contain this structural motif and has improved stability. Thus, we show that the donor polymer can be a weak link for OSC stability, which must be addressed collectively with the NFA.

This project has received funding from the European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement No. 812872 (TADFlife) and Grant Agreement No. 838885 (NarrowbandSSL). S.B. acknowledges support from the German Science Foundation (392306670/HU2362). The St Andrews team would like to thank the Leverhulme Trust (RPG-2016-047) for financial support. E.Z.-C. is a Royal Society Leverhulme Trust Senior Research fellow (SRF\R1\201089). S.M.S. acknowledges support from the Marie Skłodowska-Curie Individual Fellowship. Computational resources have been provided by the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds de la Recherche Scientifiques de Belgique (F.R.S.-FNRS) under Grant No. 2.5020.11, as well as the Tier-1 supercomputer of the Fédération Wallonie-Bruxelles, infrastructure funded by the Walloon Region under the grant agreement n1117545. Y.O. acknowledges funding by the Fonds de la Recherche Scientifique-FNRS under grant no. F.4534.21 (MIS-IMAGINE). D.B. is an FNRS Research Director. The development of efficient blue donor–acceptor thermally activated delayed fluorescence (TADF) emitters remains a challenge. To enhance the efficiency of TADF-related processes of the emitter, we targeted a molecular design that would introduce a large number of intermediate triplet states between the lowest energy excited triplet (T1) and singlet (S1) excited states. Here, we introduce an oligomer approach using repetitive donor–acceptor units to gradually increase the number of quasi-degenerate states. In our design, benzonitrile (BN) moieties were selected as acceptors that are connected together via the amine donors, acting as bridges to adjacent BN acceptors. To preserve the photoluminescence emission wavelength across the series, we employed a design based on an ortho substitution pattern of the donors about the BN acceptor that induces a highly twisted conformation of the emitters, limiting the conjugation. Via a systematic photophysical study, we show that increasing the oligomer size allows for enhancement of the intersystem crossing and reverse intersystem crossing rates. We attribute the increasing intersystem crossing rate to the increasing number of intermediate triplet states along the series, confirmed by the time-dependent density functional theory. Overall, we report Publisher PDF

Bond-free integration of two-dimensional (2D) materials yields van der Waals (vdW) heterostructures with exotic optical and electronic properties. Manipulating the splitting and recombination of photogenerated electron-hole pairs across the vdW interface is essential for optoelectronic applications. Previous studies have unveiled the critical role of defects in trapping photogenerated charge carriers to modulate the photoconductive gain for photodetection. However, the nature and role of defects in tuning interfacial charge carrier dynamics have remained elusive. Here, we investigate the nonequilibrium charge dynamics at the graphene-WS2 vdW interface under electrochemical gating by operando optical-pump terahertz-probe spectroscopy. We report full control over charge separation states and thus photogating field direction by electrically tuning the defect occupancy. Our results show that electron occupancy of the two in-gap states, presumably originating from sulfur vacancies, can account for the observed rich interfacial charge transfer dynamics and electrically tunable photogating fields, providing microscopic insights for optimizing optoelectronic devices.

Donor-acceptor (D-A) conjugated polymers are high-performance organic electronic materials that exhibit complex aggregation behavior. Understanding the solution state conformation and aggregation of conjugated polymers is crucial for controlling morphology during thin-film deposition and the subsequent electronic performance. However, a precise multiscale structure of solution state aggregates is lacking. Here, we present an in-depth small angle X-ray scattering (SAXS) analysis of the solution state structure of an isoindigo-bithiophene based D-A polymer (PII-2T) as our primary system. Modeling the system as a combination of hierarchical fibrillar aggregates mixed with dispersed polymers, we extract information about conformation and multiscale aggregation and also clarify the physical origin of features often observed but unaddressed or misinterpreted in small-angle scattering patterns of conjugated polymers. The persistence length of the D-A polymer extracted from SAXS agrees well with a theoretical model based on the dihedral potentials. Additionally, we show that the broad high q structure factor peak seen in scattering profiles can be attributed to lamellar stacking occurring within the fibril aggregates and that the low q aggregate scattering is strongly influenced by the polymer molecular weight. Overall, the SAXS profiles of D-A polymers in general exhibit a sensitive dependence on the co-existence of fibrillar aggregate and dispersed polymer chain populations. We corroborate our findings from SAXS with electron microscopy of freeze-dried samples for direct imaging of fibrillar aggregates. Finally, we demonstrate the generality of our approach by fitting the scattering profiles of a variety of D-A polymers. The results presented here establish a picture of the D-A polymer solution state structure and provide a general method of interpreting and analyzing their scattering profiles.

The importance of intermediate triplet states and the nature of excited states has gained interest in recent years for the thermally activated delayed fluorescence (TADF) mechanism. It is widely accepted that simple conversion between charge transfer (CT) triplet and singlet excited states is too crude, and a more complex route involving higher-lying locally excited triplet excited states has to be invoked to witness the magnitude of the rate of reverse inter-system crossing (RISC) rates. The increased complexity has challenged the reliability of computational methods to accurately predict the relative energy between excited states as well as their nature. Here, we compare the results of widely used density functional theory (DFT) functionals, CAM-B3LYP, LC-ωPBE, LC-ω*PBE, LC-ω*HPBE, B3LYP, PBE0, and M06-2X, against a wavefunction-based reference method, Spin-Component Scaling second-order approximate Coupled Cluster (SCS-CC2), in 14 known TADF emitters possessing a diversity of chemical structures. Overall, the use of the Tamm–Dancoff Approximation (TDA) together with CAM-B3LYP, M06-2X, and the two ω-tuned range-separated functionals LC-ω*PBE and LC-ω*HPBE demonstrated the best agreement with SCS-CC2 calculations in predicting the absolute energy of the singlet S1, and triplet T1 and T2 excited states and their energy differences. However, consistently across the series and irrespective of the functional or the use of TDA, the nature of T1 and T2 is not as accurately captured as compared to S1. We also investigated the impact of the optimization of S1 and T1 excited states on ΔEST and the nature of these states for three different functionals (PBE0, CAM-B3LYP, and M06-2X). We observed large changes in ΔEST using CAM-B3LYP and PBE0 functionals associated with a large stabilization of T1 with CAM-B3LYP and a large stabilization of S1 with PBE0, while ΔEST is much less affected considering the M06-2X functional. The nature of the S1 state barely evolves after geometry optimization essentially because this state is CT by nature for the three functionals tested. However, the prediction of the T1 nature is more problematic since these functionals for some compounds interpret the nature of T1 very differently. SCS-CC2 calculations on top of the TDA-DFT optimized geometries lead to a large variation in terms of ΔEST and the excited-state nature depending on the chosen functionals, further stressing the large dependence of the excited-state features on the excited-state geometries. The presented work highlights that despite good agreement of energies, the description of the exact nature of the triplet states should be undertaken with caution. The St Andrews team would like to thank the Leverhulme Trust (RPG-2016-047) for financial support. Computational resources have been provided by the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds de la Recherche Scientifiques de Belgique (F.R.S.-FNRS) under Grant No. 2.5020.11, as well as the Tier-1 supercomputer of the Fédération Wallonie–Bruxelles, infrastructure funded by the Walloon Region under the Grant Agreement n1117545. Y.O. acknowledges funding by the Fonds de la Recherche Scientifique-FNRS under Grant no. F.4534.21 (MIS-IMAGINE). D.B. is a FNRS Research Director. J.C.S.-G. acknowledges funding from the “Ministerio de Ciencia e Innovación” through the PID2019-106114GB-I00 project.

International audience; In the field of p-conjugated nanohoops, the size of the macrocycle has a huge impact on its structural characteristics, which in turn affect its electronic properties. In this work, we report the first experimental investigations linking the size of a nanohoop to its charge transport properties, a key property in organic electronics. We describe the synthesis and the study of the first example of cyclocarbazole possessing five constituting building units, namely [5]-cyclo-N-butyl-2,7-carbazole [5]C-Bu-Cbz. By comparison with a shorter analogue, [4]-cyclo-N-butyl-2,7-carbazole [4]C-Bu-Cbz, we detail the photophysical, electrochemical, morphological and charge transport properties, highlighting the key role played by the hoop size. Particularly, we show that the saturated field effect mobility of [5]C-Bu-Cbz is four times higher than that of its smaller analogue [4]C-Bu-Cbz (4.22 × 10-5vs 1.04 × 10-5 cm².V-1.s-1). However, the study of the other OFET characteristics (threshold voltage VTH and subthreshold slope SS) suggest that a small nanohoop is beneficial for a good organization of the molecules in thin films whereas a large one increases the density of structural defects, and hence of traps for the charge carriers. The present findings are of interest for the further development of nanohoops in electronics.

The design of semiconducting polymers with optimal charge transport characteristics has been at the crux of scientific research during the recent decades. While increase in crystalline order and planar conjugated backbones were demonstrated to be the key to success, they are not always mandatory. Sometimes, the charge carrier mobility can be enhanced by selecting conjugated backbones that are resilient to thermal fluctuations, despite leading to poor structural order. Herein, by coupling all-atom molecular dynamics simulations, electronic structure calculations, and kinetic Monte Carlo charge transport simulations, we demonstrate that the charge carrier mobility in amorphous donor-acceptor conjugated polymers is controlled by the density and quality of close-contact points between the chains and that the latter varies with the size of the donor block and the resulting alkyl side-chain density. We show an application of this strategy to the high-mobility poly(indacenodithiophene-alt-benzothiadiazole) (IDTBT) and poly(dithiopheneindenofluorene-alt-benzothiadiazole) (TIFBT) copolymers.

Electronic structure calculations unveil structure-property relationships in doped polymers: dopants inserted in the alkyl chains are stronger electron acceptors than those in conjugated backbones, leading to integer charge transfer complexes.

International audience; Graphene quantum dots, atomically precise nanopieces of graphene, are promising nanoobjects with potential applications in various domains such as photovoltaics, quantum light emitters or bio-imaging. Despite their interesting prospects, precise reports on their photophysical properties remain scarce. Here, we report on a study of the photophysics of C$_{96}$H$_{24}$(C$_{12}$H$_{25}$) graphene quantum dots. A combination of optical studies down to the single molecule level with advanced molecular modeling demonstrates the importance of the coupling to vibrations in the emission process. Optical fingerprints for H-like aggregates are identified. Our combined experimental-theoretical investigations provide a comprehensive description of the light absorption and emission properties of nanographenes, which not only represents an essentiel step towards precise control of sample production, but also paves the way for new exciting physics focused on twisted graphenoid.

Structurally precision graphene nanoribbons (GNRs) are promising candidates for next-generation nanoelectronics due to their intriguing and tunable electronic structures. GNRs with hybrid edge structures often confer them unique geometries associated with exotic physicochemical properties. Herein, a novel type of cove-edged GNRs with periodic short zigzag-edge segments is demonstrated. The bandgap of this GNR family can be tuned using an interplay between the length of the zigzag segments and the distance of two adjacent cove units along the opposite edges, which can be converted from semiconducting to nearly metallic. A family member with periodic cove-zigzag edges based on N = 6 zigzag-edged GNR, namely 6-CZGNR-(2,1), is successfully synthesized in solution through the Scholl reaction of a unique snakelike polymer precursor (10) that is achieved by the Yamamoto coupling of a structurally flexible S-shaped phenanthrene-based monomer (1). The efficiency of cyclodehydrogenation of polymer 10 toward 6-CZGNR-(2,1) is validated by FT-IR, Raman, and UV-vis spectroscopies, as well as by the study of two representative model compounds (2 and 3). Remarkably, the resultant 6-CZGNR-(2,1) exhibits an extended and broad absorption in the near-infrared region with a record narrow optical bandgap of 0.99 eV among the reported solution-synthesized GNRs. Moreover, 6-CZGNR-(2,1) exhibits a high macroscopic carrier mobility of ∼20 cm2 V-1 s-1 determined by terahertz spectroscopy, primarily due to the intrinsically small effective mass (m*e = m*h = 0.17 m0), rendering this GNR a promising candidate for nanoelectronics. ispartof: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY vol:144 issue:1 pages:228-235 ispartof: location:United States status: published

Synthesis, polymorph investigation, crystallographic study, and fabrication of OFETs in solution-processed thin films of C7-BTBT-C7.

The importance of intermediate triplet states and the nature of excited states has gained interest in recent years for the thermally activated delayed fluorescence (TADF) mechanism. It is widely accepted that simple conversion between charge transfer (CT) triplet and singlet excited states is too crude, and a more complex route involving higher-lying locally excited triplet excited states has to be invoked to witness the magnitude of the rate of reverse intersystem crossing (RISC) rates. The increased complexity has challenged the reliability of computational methods to accurately predict the relative energy between excited states as well as their nature. Here we compare the results of widely used DFT functionals, CAM-B3LYP, LC-ꞷPBE, LC-ꞷ*PBE, LC-ꞷ*HPBE, B3LYP, PBE0 and M06-2X against a wavefunction-based reference method, Spin-Component Scaling second-order approximate Coupled-Cluster (SCS-CC2) in fourteen known TADF emitters possessing a diversity of chemical structures. Overall, the use of the Tamm-Dancoff Approximation (TDA) together with the CAM-B3LYP, M06-2X and the two ꞷ-tuned range-separated functionals LC-ꞷ*PBE and LC-ꞷ*HPBE demonstrated the best agreement with SCS-CC2 calculations in predicting the absolute energy of the singlet S1, and triplet T1 and T2 excited states and their energy differences. However, consistently across the series and irrespective of the functional or the use of TDA, the nature of T1 and T2 is not as accurately captured as compared to S1. The presented work highlights that despite good agreement of energies, the description of the exact nature of the triplet states should be undertaken with caution.

We show how borylation of an acceptor-donor-acceptor (A-D-A) thermally activated delayed fluorescence (TADF) emitter, DIDOBNA-N, transforms the compound into a multi-resonant TADF (MR-TADF) emitter, MesB-DIDOBNA-N. DIDOBNA-N emits bright blue light (𝜆PL = 444 nm, FWHM = 64 nm, 𝛷PL = 81%, 𝜏d = 23 𝜇s, 1.5 wt% in TSPO1). The deep blue organic light-emitting diode (OLED) based on this compound shows a very high maximum external quantum efficiency (EQEmax) of 15.3% for a device with CIEy of 0.073. The MR-TADF emitter, MesB-DIDOBNA-N shows efficient and narrowband violet emission (𝜆PL = 402 nm, FWHM = 19 nm, 𝛷PL = 74.7%, 𝜏d = 133 𝜇s, 1.5 wt% in TSPO1). The OLED with MesB-DIDOBNA-N shows out-standing efficiency for a violet OLED at 9.3% and CIEy = 0.044, which is the bluest EL reported for a MR-TADF OLED to date. Noteworthy are the CIE coordinates of (0.166, 0.045), which are very close to the Rec.2020 standard for blue (0.131, 0.046). The EQEmax values were improved from 9.3% to 13.6% by increasing the concentration of the emitter in the host from 1.5 wt% to 5 wt%.

This project has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska Curie grant agreement No 838885 (NarrowbandSSL) and under the Marie Skłodowska Curie grant agreement No 812872 (TADFlife). S.M.S. acknowledges support from the Marie Skłodowska-Curie Individual Fellowship (grant agreement No 838885 NarrowbandSSL). The St. Andrews team would like to thank the Leverhulme Trust (RPG-2016-047) for financial support. E. Z.-C. is a Royal Society Leverhulme Trust Senior Research fellow (SRF\R1\201089). Computational resources have been provided by the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds de la Recherche Scientifiques de Belgique (F. R. S.-FNRS) under Grant No. 2.5020.11, as well as the Tier-1 supercomputer of the Fédération Wallonie-Bruxelles, infrastructure funded by the Walloon Region under the grant agreement n 1117545. Developing high-efficiency purely organic blue organic light-emitting diodes (OLEDs) that meet the stringent industry standards is a major current research challenge. Hyperfluorescent device approaches achieve in large measure the desired high performance by combining the advantages of a high-efficiency thermally activated delayed fluorescence (TADF) assistant dopant with a narrowband deep-blue multi-resonant TADF (MR-TADF) terminal emitter. However, this approach requires suitable spectral overlap to support Förster resonance energy transfer (FRET) between the two. Here, a color tuning of a recently reported MR-TADF B,N-heptacene core through control of the boron substituents is demonstrated. While there is little impact on the intrinsic TADF properties—as both singlet and triplet energies decrease in tandem—this approach improves the emission color coordinate as well as the spectral overlap for blue hyperfluorescence OLEDs (HF OLEDs). Crucially, the red-shifted and more intense absorption allows the new MR-TADF emitter to pair with a high-performance TADF assistant dopant and achieve maximum external quantum efficiency (EQEmax) of 15% at color coordinates of (0.15 and 0.10). The efficiency values recorded for the device at a practical luminance of 100 cd m–2 are among the highest reported for HF TADF OLEDs with CIEy ≤ 0.1. Publisher PDF

Herein, we reported an ultrapure blue multiple-resonance-induced thermally activated delayed fluorescence (MR-TADF) material (ν-DABNA-O-Me) with a high photoluminescence quantum yield and a large rate constant for reverse intersystem crossing. Because of restricted π-conjugation of the HOMO rather than the LUMO induced by oxygen atom incorporation, ν-DABNA-O-Me shows a hypsochromic shift compared to the parent MR-TADF material (ν-DABNA). An organic light-emitting diode based on this material exhibits an emission at 465 nm, with a small full-width at half-maximum of 23 nm and Commission Internationale de l'Eclairage coordinates of (0.13, 0.10), and a high maximum external quantum efficiency of 29.5 %. Moreover, ν-DABNA-O-Me facilitates a drastically improved efficiency roll-off and a device lifetime compared to ν-DABNA, which demonstrates significant potential of the oxygen atom incorporation strategy.

Two new deep-blue narrowband multi-resonant emitters, 1B-DTACrs and 2B-DTACrs, one of which shows thermally activated delayed fluorescence (TADF), based on boron, nitrogen, and oxygen doped nanographenes are reported. Devices based on 2B-DTACrs showed an EQE

This work was supported financially by the JSPS Core-to-Core Program (grant number: JPJSCCA20180005) and Kyulux Inc. S. M. S. acknowledges support from the Marie Skłodowska-Curie Individual Fellowship (grant agreement No 838885 NarrowbandSSL). We would like to thank the Leverhulme Trust (RPG-2016-047) for financial support. E. Z.-C. is a Royal Society Leverhulme Trust Senior Research fellow (SRF\R1\201089). We thank the EPRSC for funding (EP/R035164/1). Computational resources have been provided by the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds de la Recherche Scientifiques de Belgique (F. R. S.-FNRS) under Grant No. 2.5020.11, as well as the Tier-1 supercomputer of the Fédération Wallonie-Bruxelles, infrastructure funded by the Walloon Region under the grant agreement n1117545. Y. O. acknowledges funding by the Fonds de la Recherche Scientifique-FNRS under Grant no. F.4534.21 (MIS-IMAGINE). D. B. is a FNRS Research Director. Two new deep-blue narrowband multi-resonant emitters, 1B-DTACrs and 2B-DTACrs, one of which shows thermally activated delayed fluorescence (TADF), based on boron, nitrogen, and oxygen doped nanographenes are reported. Devices based on 2B-DTACrs showed an EQEmax of 14.8% and CIE coordinates of (0.150, 0.044), which are very close to the BT.2020 requirement for blue pixels. Publisher PDF

Graphitic carbon nitride (gCN) is an important heterogeneous metal-free catalytic material. Thermally induced post-synthetic modifications, such as amorphization and/or reduction, were recently used to enhance the photocatalytic response of these materials for certain classes of organic transformations, with structural defects possibly playing an important role. The knowledge of how these surface modifications modulate the photocatalytic response of gCN is therefore not only interesting from a fundamental point of view, but also necessary for the development and/or tuning of metal-free gCN systems with superior photo-catalytic properties. Herein, employing density functional theory calculations and combining both the periodic and molecular approaches, in conjunction with experimental EPR measurements, we demonstrate that different structural defects on the gCN surface generate distinctive radical defect states localized within the electronic bandgap, with only those correlated with amorphous and reduced gCN structures being photo-active. To this end, we (i) model defective gCN surfaces containing radical defect states; (ii) assess the interactions of these defects with the radical precursors involved in the photo-driven alkylation of electron-rich aromatic compounds (namely perfluoroalkyl iodides); and (iii) describe the photo-chemical processes triggering the initial step of that reaction at the gCN surface. We provide a coherent structure/photo-catalytic property relationship on defective gCN surfaces, elaborating how only specific defect types act as binding sites for the perfluoroalkyl iodide reagent and can favor a photo-induced charge transfer from the gCN surface to the molecule, thus triggering the perfluoroalkylation reaction.

Recent years have shown an increasing number of studies dedicated to new light emitters for diverse applications such as optoelectronics, bio-imaging, and quantum technologies. In this context, graphene quantum dots (GQD) have important assets since bottom-up chemistry allows complete control of the structure, opening the way to wide customization of their electronic, optical, and spin properties [1-3]. The full benefit from these opportunities requires addressing GQD’s intrinsic photophysical properties.To do so, single molecule photoluminescence experiment is a powerfull tool [4]. Here, we highlight the influence of vibrations on GQDs’ optical properties, by comparing optical studies to extensive DFT/TDDFT calculations combined with molecular dynamics simulations. Specifically, we discussed their role in the transitions' oscillator strengths [5]. In order to get deeper in the photophysics of GQD, we investigate the spectroscopy of single GQDs at cryogenic temperatures. In particular, we show a narrowing of the emission lines at low temperature, that allows us to characterize and identify vibrational replicas that are characteristic to GQDs [6]. [1] M. G. Debije, J. Am. Chem. Soc. 2004, 126, 4641 [2] X. Yan, X. Cui, and L.-s. Li, J. Am. Chem. Soc. 2010 132, 5944 [3] A. Konishi et al, J. Am. Chem. Soc. 2010, 132, 11021 [4] S. Zhao et al, Nature Communications, 2018, 9, 3470 [5] T. Liu et al, under review [6] T. Liu et al, in preparation

The lattice dynamics of organic semiconducting crystals has a significant role in determining their electronic and mechanical properties. A common technique to control these macroscopic properties is chemically modifying the molecular structure. These modifications are known to change the molecular packing, but their effect on the lattice dynamics is relatively unexplored though it can be equally important to their performance at finite temperatures. Therefore, we investigate how chemical modifications to a core [1]benzothieno[3,2-b]benzothiophene (BTBT) semiconducting crystal affect the evolution of the crystal structural dynamics with temperature. Our study combines temperature-dependent polarization-orientation (PO) low-frequency Raman measurements with first-principles calculations and single-crystal XRD measurements. We show that the chemical modifications can indeed suppress expressions of vibrational anharmonicity in the lattice dynamics. Specifically, we detect in BTBT a gradual change in the PO Raman response with temperature, indicating a unique expression of anharmonicity. This anharmonic expression is suppressed in all examined chemically modified crystals (ditBu-BTBT and diC8-BTBT, diPh-BTBT, and DNTT). Our findings indicate that π-conjugated chemical modifications suppress anharmonic effects more effectively than alkyl chains.

The St Andrews team would like to thank the Leverhulme Trust (RPG-2016-047) for financial support. E. Z.-C. is a Royal Society Leverhulme Trust Senior Research fellow (SRF\R1\201089). Computational resources have been provided by the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds de la Recherche Scientifiques de Belgique (F.R.S.-FNRS) under Grant No. 2.5020.11, as well as the Tier-1 supercomputer of the Fédération Wallonie-Bruxelles, infrastructure funded by the Walloon Region under the grant agreement n1117545. G.R. acknowledges a grant from the “Fonds pour la formation à la Recherche dans l’Industrie et dans l’Agriculture” (F.R.I.A.) of the F.R.S.-F.N.R.S. Y.O. acknowledges funding by the Fonds de la Recherche Scientifique-FNRS under Grant n° F.4534.21 (MIS-IMAGINE). D.B. is a FNRS Research Director. J.C.S.G. acknowledges “Ministerio de Ciecia e Innovación” of Spain (PID2019-106114GB-I00). With the surge of interest in multiresonant thermally activated delayed fluorescent (MR-TADF) materials, it is important that there exist computational methods to accurately model their excited states. Here, building on our previous work, we demonstrate how the spin-component scaling second-order approximate coupled-cluster (SCS-CC2), a wavefunction-based method, is robust at predicting the ΔEST (i.e., the energy difference between the lowest singlet S1 and triplet T1 excited states) of a large number of MR-TADF materials, with a mean average deviation (MAD) of 0.04 eV compared to experimental data. Time-dependent density functional theory calculations with the most common DFT functionals as well as the consideration of the Tamm-Dancoff approximation (TDA) consistently predict a much larger ΔEST as a result of a poorer account of Coulomb correlation as compared to SCS-CC2. Very interestingly, the use of a metric to assess the importance of higher order excitations in the SCS-CC2 wavefunctions shows that Coulomb correlation effects are substantially larger in the lowest singlet compared to the corresponding triplet and need to be accounted for a balanced description of the relevant electronic excited states. This is further highlighted with coupled cluster singles-only calculations, which predict very different S1 energies as compared to SCS-CC2 while T1 energies remain similar, leading to very large ΔEST, in complete disagreement with the experiments. We compared our SCS-CC2/cc-pVDZ with other wavefunction approaches, namely, CC2/cc-pVDZ and SOS-CC2/cc-pVDZ leading to similar performances. Using SCS-CC2, we investigate the excited-state properties of MR-TADF emitters showcasing large ΔET2T1 for the majority of emitters, while π-electron extension emerges as the best strategy to minimize ΔEST. We also employed SCS-CC2 to evaluate donor–acceptor systems that contain a MR-TADF moiety acting as the acceptor and show that the broad emission observed for some of these compounds arises from the solvent-promoted stabilization of a higher-lying charge-transfer singlet state (S2). This work highlights the importance of using wavefunction methods in relation to MR-TADF emitter design and associated photophysics. Postprint

Electrochemical proton storage plays an essential role in designing next-generation high-rate energy storage technologies, e.g., aqueous batteries. Two-dimensional conjugated covalent organic frameworks (2D c-COFs) are promising electrode materials, but their competitive proton and metal-ion insertion mechanisms remain elusive, and COF-based proton storage is rarely explored. Here, we report a perinone-based ladder-type 2D c-COF towards fast proton storage in both mild aqueous Zn-ion electrolyte and strong acid. We unveil that the generated C-O- groups via discharge exhibit largely reduced basicity due to the considerable pi-delocalization in perinone, thus affording the 2D c-COF a unique affinity to proton with fast kinetics. As a consequence, the 2D c-COF electrode presents outstanding rate capability up to 200 A g-1 (over 2500C). Our work reports the first example of proton storage among COFs and highlights the great potential of perinone-based 2D c-COF in future energy devices.

Two new deep-blue narrowband multi-resonant emitters, 1B-DTACrs and 2B-DTACrs, one of which showing thermally activated delayed fluorescence (TADF), based on boron, nitrogen, and oxygen doped nanographenes were designed and synthesized in good yields. Precise control of the extent of borylation was achieved by modulating the reaction temperature and stoichiometry of the Lewis acid in the reaction. A comprehensive structural, theoretical, photophysical, electrochemical, and electroluminescent study is presented. Both emitters possess high photoluminescence quantum yields of up to 83%, small full width at half maximums (FWHMs) of around 24 nm, and deep blue emissions of around 450 nm in mCBP films. Devices based on 2B-DTACrs showed high maximum external quantum effi-ciencies of 14.8% and a deep-blue emission at 447 nm together with Commission Internatio-nale de l’Éclairage coordinates of (0.150, 0.044), which are very close to the BT.2020 re-quirement for blue pixels.

We report on computational studies of the potential of three borane Lewis acids (LAs) (B(C6F5)3 (BCF), BF3, and BBr3) to form stable adducts and/or to generate positive polarons with three different semiconducting π-conjugated polymers (PFPT, PCPDTPT and PCPDTBT). Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations based on range-separated hybrid (RSH) functionals provide insight into changes in the electronic structure and optical properties upon adduct formation between LAs and the two polymers containing pyridine moieties, PFPT and PCPDTPT, unravelling the complex interplay between partial hybridization, charge transfer and changes in the polymer backbone conformation. We then assess the potential of BCF to induce p-doping in PCPDTBT, which does not contain pyridine groups, by computing the energetics of various reaction mechanisms proposed in the literature. We find that reaction of BCF(OH2) to form protonated PCPDTBT and [BCF(OH)]−, followed by electron transfer from a pristine to a protonated PCPDTBT chain is highly endergonic, and thus unlikely at low doping concentration. The theoretical and experimental data can, however, be reconciled if one considers the formation of [BCF(OH)BCF]− or [BCF(OH)(OH2)BCF]− counterions rather than [BCF(OH)]− and invokes subsequent reactions resulting in the elimination of H2., Here we report on DFT calculations investigating the mechanistic aspects in doping organic semiconductors by the use of Lewis acids. Our results highlight the role played by the formation of diboron-containing bridged anions in the doping mechanism.

Transition metal dichalcogenides (TMDCs) are emerging as promising two-dimensional (2D) materials. Yet, TMDCs are prone to inherent defects such as chalcogen vacancies, which are detrimental to charge transport. Passivation of these vacancies via molecular functionalization is an efficient strategy, not only to heal the active defects and improve the charge transport characteristics of TMDCs, but also to engineer their properties by appropriate selection of the passivating molecules. Herein, Density-Functional Theory (DFT) calculations are combined with ab initio Molecular Dynamics (abMD) simulations to elucidate the mechanism of molecular passivation in defective WS2 and WSe2 monolayers containing chalcogen vacancies that are functionalized with thiophenol molecules. We demonstrate that functionalized thiophenol molecules act as molecular dopants inducing n-/p- type doping in defective WS2 and WSe2 monolayers, in addition to healing the electronic mid-gap defect states caused by the chalcogen vacancies in a dynamic way. The electron donating and/or withdrawing nature of passivating thiophenol molecules is found to modulate both the amount of dipole induced doping in defective TMDCs and the magnitude of their interaction strength, which in-turn govern the extent of dynamic defect healing and subsequent recovery of the electronic band structure in defect passivated TMDCs.