Donor Molecules Research Articles

Origin of the intermolecular forces that produce donor–acceptor stacks in π-conjugated charge-transfer complexes

The attraction between π-conjugated planar electron donor and acceptor molecules that form many stable charge-transfer (CT) complexes has been explained by quantum chemical CT interactions, although the fundamental origin remains unclear. Here, we demonstrate the mechanism of CT complex formation by potential energy map analysis for TTF–CA and BTBT–TCNQ, using energy decomposition of intermolecular interaction by symmetry-adapted perturbation theory (SAPT) combined with coupled cluster calculation. We find that the source of attraction between donor and acceptor molecules is ascribed primarily to the dispersion force and also to the electrostatic force. In contrast, the contribution of CT interactions to the attractive forces is minimal. We demonstrate that the highly directional feature of the exchange repulsion force, coupled with the attractive dispersion and electrostatic forces, is crucial in determining the intermolecular arrangements of actual CT crystals. These findings are key for understanding the unique structural and electronic properties of π-conjugated CT complexes.

Charge-Transfer Interactions Between Antibiotics and Small Organic Acids: Spectroscopic Characterization and Computational Investigation

Six new charge-transfer complexes using ofloxacin (OFL) and sulfamethazine (SMR) as electron donors and coumaric acid (COA), cinnamic acid (CNA), and salicylic acid (SAA) as acceptors via equimolar mixture have been synthesized. The experiment used UV-vis spectroscopy to determine the formation of the complex in methanol through the presence of a new broad absorption band with a maximum wavelength in the 200-400 nm range. The molecular composition of the charge-transfer complexes was determined by the spectrophotometric titration method and found to be 1:1 (donor: acceptor). These complexes have been characterized by infrared (FTIR) and scanning electron microscopy (SEM). In the FTIR spectra, the CT complexes showed a wavelength shift compared to the reactants. The complexes exhibited various morphologies by SEM, including spherical particles, short rods, and flattened shapes. Additionally, quantum chemical calculations at the DFT/B3LYP level of theory investigated the complexes' steady-state structures, energies, and charge densities. The intermolecular binding energies was negative, indicating that the reactions of the six complexes proceeded spontaneously. There was strong van der Waals forces and hydrogen bonds between the donor and acceptor, which contributed to the complexes' strong molecular stability. The C-N and N-H groups in the donor molecule, and the -COOH group in the acceptor molecule, played key roles in the complexation process. DFT calculation results were appropriate to support our experimental results. This study highlights the molecular mechanisms of donor and acceptor action in charge-transfer interactions, providing a theoretical basis for the synthesis of antibiotic complexes and the removal of antibiotics.

Photomodulation of Charge Transfer through Excited‐State Processes: Directing Donor‐Acceptor Binding Dynamics

AbstractModulating charge transfer (CT) interactions between donor and acceptor molecules may give rise to unique dynamic changes in physicochemical properties, exhibiting great importance in supramolecular chemistry and materials science. In this work, we demonstrate the first instance of reversible photomodulation of donor‐acceptor (D−A) CT interaction in the solid state. Pyridinium‐based chromophore featuring π‐conjugated D−A structures can not only function as a good electron acceptor to undergo photoinduced electron transfer (ET) or engage in intermolecular CT interaction, but also exhibit unique dual emission depending on the excitation wavelengths. The rotatable C−C single bonds within D−A pairs enhance the tunability of molecular structure. Through the synergy of a photoinduced ET and an excited‐state conformational change, the intermolecular CT interaction can be switched on and off by alternate light irradiation to enable reversibly modulation of the affinity between donor and acceptor molecules, accompanied by visual color switching and fluorescence on‐off as feedback signals.

Discovery of a novel methionine biosynthetic route via O-phospho-l-homoserine.

Methionine (Met), a sulfur-containing amino acid, is essential for the underlying biological processes in living organisms. In addition to its importance as a starting building block for peptide chain elongation in protein biosynthesis, Met is a direct precursor of S-adenosyl-l-methionine, an indispensable methyl donor molecule in primary and secondary metabolism. Streptomyces bacteria are well known to produce diverse secondary metabolites, but many strains lack canonical Met pathway genes for l-homocysteine, a direct precursor of Met in bacteria, plants, and archaea. Here, we report the identification of a novel gene (metM) responsible for the Met biosynthesis in Streptomyces strains and demonstrate the catalytic function of the gene product, MetM. We further identified the metO gene, a downstream gene of metM, and showed that it encodes a sulfur-carrier protein (SCP). In in vitro analysis, MetO was found to play an important role in a sulfur donor by forming a thiocarboxylated SCP. Together with MetO (thiocarboxylate), MetM directly converted O-phospho-l-homoserine to l-homocysteine. O-Phospho-l-homoserine is also known as an intermediate for threonine biosynthesis in bacteria and plants, and MetM shares sequence homology with threonine synthase. Our findings thus revealed that MetM seizes O-phospho-l-homoserine from the threonine biosynthetic pathway and uses it as an intermediate of the Met biosynthesis to generate the sulfur-containing amino acid. Importantly, this MetM/MetO pathway is highly conserved in Streptomyces bacteria and distributed in other bacteria and archaea.IMPORTANCEMethionine (Met) is a sulfur-containing proteinogenic amino acid. Moreover, Met is a direct precursor of S-adenosyl-l-methionine, an indispensable molecule for expanding the structural diversity of natural products. Because Met and its derivatives benefit humans, the knowledge of Met biosynthesis is important as a basis for improving their fermentation. Streptomyces bacteria are well known to produce diverse and valuable natural products, but many strains lack canonical Met pathway genes. Here, we identified a novel l-homocysteine synthase (MetM) in Streptomyces and demonstrated that it converts O-phospho-L-homoserine to l-homocysteine using a thiocarboxylated sulfur-carrier protein as a sulfur donor. Since the metM is distributed in other bacteria and archaea, our pioneering study contributes to understanding Met biosynthesis in these organisms.

Nitrogen Oxide (NO) in the Pathogenesis of Preeclampsia.

The concentrations of nitric oxide (NO) donors in the plasma of pregnant women with preeclampsia is several times higher than in healthy pregnant women. Antihypertensive drugs acting not through the NO-mediated mechanisms normalized BP in some women with preeclampsia, but did not significantly reduce the levels of NO donors in the plasma. It appears that preeclampsia is associated with insufficient NO availability for the targets, rather than low intensity of NO synthesis. The concentration of NO donor molecules in the plasma can therefore be a useful additional diagnostic marker of preeclampsia.

Elucidating the Advancement in the Optoelectronics Characteristics of Benzoselenadiazole-Based A2-D-A1-D-A2-Type Nonfullerene Acceptors for Efficient Organic Solar Cells.

The potential applications of nonfullerene acceptors (NFAs) such as tunable band gaps, improved charge separation, wide-range absorption, enhanced power conversion efficiency, and operational stability make them highly favorable for organic photovoltaic applications. Herein, we designed eight novel structurally modified nonfused benzoselenadiazole (BSe)-based A2-D-A1-D-A2-type NFAs for efficient organic solar cells (OSCs). These newly modeled BSe-based NFA series contain BSe as the central core. We employed strong electron-withdrawing moieties at terminal acceptor A2 to further enhance the optical, optoelectronics, and photovoltaic characteristics of OSCs. These designed molecules (HNM1-HNM8) along with the synthetic reference molecule (HNM) were thoroughly characterized by using efficient and advanced quantum chemical simulation approaches. Thus, to ascertain the enhancement of both optical and photochemical response, a thorough density functional theory (DFT) study was carried out using the M062X level in association with the 6-31G(d,p) basis set. All of the investigated molecules (HNM1-HNM8) had their excited states calculated using the time-dependent density functional theory method. The newly designed molecules (HNM1-HNM8) presented narrower band gaps, improved absorption and optoelectronics properties, and reduced excitation and binding energies. The electrostatic potential, density of states, transition density matrix, ionization potential, and electron affinity analysis of this newly designed (HNM1-HNM8) series revealed a strong coherence with those of the reference HNM molecule. Electron density difference mapping allowed us to visualize the spatial movement of electrons between the donor and acceptor molecules during excitation. This insight helps us to understand the efficiency of charge separation and recombination processes that are critical for the performance of organic photovoltaics. The reorganization energy and charge transfer analysis suggests that HNM1-HNM8 molecules could act as NFAs for organic photovoltaic applications to enhance their efficiency further. The donor: acceptor charge transfer analysis was also carried out, which revealed that the PTB7-Th:HNM2 donor:acceptor complex shows a great charge transportation process at the donor-acceptor interface. Moreover, the photovoltaic analysis shows that the designed (HNM1-HNM8) NFA series has a great potential to produce improved open-circuit voltage and fill factor values, which may be helpful in enhancing the overall PCEs of the OSCs.

Development and evaluation of nanostructured systems for cutaneous delivery of H2S-releasing corticosteroids for skin inflammatory diseases

Psoriasis is an immune-mediated chronic inflammatory disease that causes major psychosocial impact. Topical corticosteroids represent the standard pharmacological treatment for mild-to-moderate disease, but their local and systemic adverse effects reinforce the need for treatment innovations. Here we developed lamellar phase-based formulations for topical delivery of a hybrid dexamethasone and hydrogen sulfide (H2S) donor molecule (Dexa-TBZ), aiming to potentiate the effects of the glucocorticoid with H2S. They offer the possibility to obtain precursor formulations free of water that originate lamellar phases upon water addition, preventing drug hydrolysis during storage. Two groups of formulations were developed varying the surfactants and oil phase types and content. Systems containing 20 and 70 % of water formed, respectively, bulk lamellar phase and a more fluid formulation consisting of dispersed droplets (< 1000 nm) stabilized by lamellar phase. Both presented pseudoplastic behavior. Dexa-TBZ was incorporated at 1 %, remaining stable for 8 h. Drug content decreased to ∼80 % after 1 week in precursor formulations free of water, but remained stable after that. Without causing changes to the cutaneous barrier function ex vivo or to the histological structure of the skin in vivo, the formulation containing phosphatidylcholine as surfactant and 70 % of water promoted 1.8- and 2.7-fold increases in Dexa-TBZ penetration in the stratum corneum and epidermis+dermis, respectively, compared to a control solution, demonstrating their potential applicability as topical delivery systems.

Design of N-doped C60-σ-B-doped C60 photodetector based on resonant tunneling diode using DFT and NEGF method.

Photodetectors utilizing donor/acceptor (D/A) molecules have the capacity to detect light through molecular interactions between a donor and an acceptor molecule. These devices leverage electronic or optical changes within molecules when exposed to light, resulting in observable modifications. The unique properties of photodetectors with D/A molecules make them valuable tools in various fields, including molecular electronics. This paper presents the modeling and simulation of a single-molecule photodetector based on a D/A molecule configuration. The acceptor molecule used is N-doped C60 fullerene, while the donor molecule is B-doped C60 fullerene. Initially, simulations were conducted at zero bias voltage to determine the energy and states of the bipartite molecule. Subsequently, the system's Hamiltonian was computed based on these results. The self-consistent field method (SCF) and optical self-energy coefficients were employed for modeling. Finally, the current-voltage curve of the device was derived for various input light frequencies. The simulation and modeling results demonstrated that the device exhibited negative differential resistances at bias voltages of 0.33 V, 1.58 V, and - 0.93 V, depending on the input light frequency. Furthermore, the designed device demonstrated the ability to detect and absorb waves with different frequencies. The number of current peaks in the current-voltage curve varied with by altering the number of optical modes. The computational work was conducted using the software package of Atomistix ToolKit (ATK-2018.06) and MATLAB code. The calculations were based on the density functional theory (DFT) approach and the self-consistent field method, specifically the non-equilibrium Green function (NEGF). The exchange correlation function was investigated using the generalized gradient approximation (GGA) proposed by Perdew, Burke, and Ernzerhof (PBE). For the calculations, we employed the double-ζ plus polarization (DZP) basis set. Initially, the structures of N doped-C60-σ-B-doped-C60 molecule underwent optimization using the DFT approach implemented in the ATK package. This optimization process allowed us to extract the parameters of the molecule. Subsequently, we utilized the NEGF formalism in MATLAB software to model and simulate photodetector based on the optimized molecule. We calculated important features of the photodetector, such as photocurrent, and compared the performance of the photodetector using photons with energies of 2 and 3 eV.

Synergistic charge-transfer dynamics of novel benzothiadiazole-based donor materials for higher power conversion efficiency: From structural engineering to efficiency assessment in non-fullerene organic solar cells

In the realm of organic solar cell technology, current research is dedicated to enhancing the photovoltaic properties of donor-π-acceptor (D-π-A) materials to achieve higher power conversion efficiencies (PCE). This optimization focuses particularly on fine-tuning the conduction band and electrolytic characteristics to maximize performance. Addressing the growing demand for novel materials with enhanced optoelectronic properties in organic photovoltaic research, our proposed compound BT05, one of nine new benzothiadiazole-based D-π-A donor molecules (BT01-BT09), exhibits a power conversion efficiency (PCE) of 25%, surpassing the 18% PCE of the reference compound BTD-OMe. TD-DFT and DFT simulations illuminate how donor modifications enhance the photovoltaic characteristics of the proposed molecules. Higher open-circuit voltage (VOC) of 1.74-2.26 V, increase in binding energy (∼1.997), λmax (470-476 nm), reduction in energy gap (4.25-4.65 eV), also validates the PCE results and confirm the usefulness of designed molecules (BT01-BT09). Moreover, DHOMO and ALUMO, TDM, reorganization energy λe (0.0124-0.0134) and λh (0.0094-0.0098), and NPA results also confirm that BT01-BT09 molecules unlock the organic solar cell's potential and advance sustainable energy solutions through innovative technology. Among all developed compounds, BT05 displays higher VOC (2.26 V), 87% fill-factor, and 25% PCE; hence, it is recommended in future solar cell applications.

Electron-electron-ion triple-coincidence experiment of electron-initiated valence ionization of small water clusters

The ionization and fragmentation of small water clusters induced by electron impact (80 eV) is investigated. Using a multiparticle coincidence spectrometer (reaction microscope), all three charged final state particles—two outgoing electrons and one fragment ion—are detected. Nonprotonated (H2O)2+ and protonated water clusters H3O+, [H2O]2H+, [H2O]4H+, and [H2O]5H+ are identified in the measured ion spectrum. The ionization channels for formation of these species are investigated by measuring the kinetic energy distributions and the electronic states of the ions. Only a single state can lead to (H2O)2+, which is identified as ionization of water dimer with a 1b1 hole at the hydrogen bonding donor molecule, while for the protonated water species three major electronic states corresponding to the ionization of 1b1, 3a1, and 1b2 type orbitals are observed. Published by the American Physical Society 2024

Two pressure-induced molecular superconductors with different types of crystal and electronic structures derived from an unsymmetrical tetrachalcogenafulvalene

Abstract We newly synthesized an organic donor molecule ETTM-STF (ethylenedithio(trimethylene)diselenadithiafulvalene), a molecular hybrid of HMTTF (hexamethylenetetrathiafulvalene) and BETS (bis(ethylenedithio)tetraselenafulvalene). Electrochemical oxidation of ETTM-STF provided two cation radical salts, (ETTM-STF)2Au(CN)2 and (ETTM-STF)2BF4. Crystal structure of the Au(CN)2 salt is characterized by a monolayer structure based on dimerized donor molecules. On the other hand, the BF4 salt shows a bilayer structure that is composed of two crystallographically independent conducting layers with different types of electronic structures. At ambient pressure, the Au(CN)2 salt is a Mott insulator and the BF4 salt undergoes a metal–nonmetal transition where the two types of conducting layers exhibit different behavior. Application of pressure suppressed the nonconducting behavior and induced a superconducting state in the Au(CN)2 salt (Tc = 3.4 K at 9.5 kbar) and in the BF4 salt (Tc = 6.8 K at 8 kbar).

Boron-bridged bis(tetrathiafulvalene) zwitterionic neutral radical conductors: substituent effects on intramolecular and intermolecular electronic interactions and physical properties

Abstract We have recently proposed a new molecular design for neutral radical molecular conductors, based on the chemical composition of D2X-type charge-transfer salts (D = π-electron donor molecule, X = monovalent anion). Namely, we connected two tetrathiafulvalene (TTF)-based π-electron skeletons having a charge of +0.5 via a boron anion B–, to obtain a purely organic zwitterionic neutral radical {[(PDT-TTF-Cat)2]+B–}• that shows unique electronic states and properties in the crystal due to the intramolecular and intermolecular interactions of the +0.5-charged π-skeletons. In order to further explore the structural and electronic features of this kind of zwitterionic neutral radical conductor, in this study, we have examined chemical modifications to {[(PDT-TTF-Cat)2]+B–}•. As a result, an analog molecule {[(BMT-TTF-Cat)2]+B–}•, in which propylenedithio (PDT) groups on the TTF terminals in {[(PDT-TTF-Cat)2]+B–}• are replaced by bis(methylthio) ones, was successfully synthesized as air-stable single crystals. Interestingly, this chemical modification causes intramolecular charge disproportionation between the two TTF-based π-skeletons (i.e. the monovalent cation radical TTF+• and the neutral TTF0) coupled to the modulation of the intermolecular distances and interactions between these π-skeletons, leading to electrical and magnetic properties significantly different from those of the crystal of {[(PDT-TTF-Cat)2]+B–}•.

SYNTHESIS AND APPLICATION OF PHOSPHINITE LIGAND-CONTAINING RUTHENIUM CATALYSTS IN TRANSFER HYDROGENATION

Transfer hydrogenation (TH) is a highly significant reaction in organic chemistry, especially in the synthesis of pharmaceuticals, agrochemicals, and fine chemicals. This method involves the transfer of hydrogen from a donor molecule to an unsaturated substrate, offering a safer and more convenient alternative to direct hydrogenation, which typically requires high-pressure hydrogen gas. TH stands out for its ability to selectively reduce multiple functional groups under milder conditions, thereby reducing the risk of overreduction or damage to sensitive functional groups. This technique is particularly valuable in asymmetric synthesis (AS), where chiral catalysts enable the production of enantiomerically pure compounds, crucial for drug development.Ruthenium complexes are particularly noteworthy for their effectiveness in asymmetric TH. Their stability and adaptability to different reaction environments make them ideal for both laboratory-scale and industrial applications. Phosphinite ligands (P(OR)R'2) are used in synthesis of complexes to improve their properties. These ligands are known for their ability to finely tune the electronic and steric properties of metal centers. The electron-donating nature of the phosphorus atom, combined with the variability in the R and R' groups, allows for significant customization of the catalyst's properties.The purpose of the work is to review up-to-date discoveries in the field of TH.The integration of phosphinite ligands into ruthenium catalysts marks a significant advancement in the field of TH. These catalysts exhibit enhanced efficiency, selectivity, and stability, proving crucial in AS. The study's exploration of various hydrogen sources, bases, and mechanisms has provided deeper insight into the process of TH.

An Artificial Light-Harvesting System based on Supramolecular AIEgen Assembly.

Photosynthesis is a complex multi-step process in which light collection is the initial step of photosynthesis and plays an important role in the utilization of solar energy. In order to improve the utilization of sunlight, researchers have developed a variety of artificial light-harvesting systems to simulate photosynthesis in nature. Here, we report a supramolecular artificial light-harvesting system in aqueous solution. Since β-cyclodextrin (β-CD) has a hydrophobic cavity and a hydrophilic outer surface, we adopt β-cyclodextrin (β-CD) as the host molecule and use adamantane as the guest molecule. At the same time, we modified β-CD with the donor molecule naphthalimide and adamantane with the tetraphenylethylene molecule which has aggregation-induced emission (AIE) effects. By using fluorescent molecules with AIE, the self-quenching effect caused by aggregation in aqueous solution can be effectively avoided. Due to the host-guest interaction of β-CD and adamantane, nanoparticles with stable structure and uniform size can be spontaneously assembled in water. Because of the close distance and strong spectral overlap between naphthalimide and tetraphenylethylene, Förster resonance energy transfer (FRET) was realized, and artificial light-harvesting system was successfully constructed in aqueous solution. Therefore, this study provides a new strategy for constructing artificial light-harvesting system, and the artificial light-harvesting system shows broad application prospects in aqueous solutions.

Theoretical investigation of benzodithiophene-based donor molecules in organic solar cells: from structural optimization to performance metrics.

Achieving high power conversion efficiency (PCE) remains a significant challenge in the advancement of organic solar cells (OSCs). In the field of organic photovoltaics (OPVs), considerable progress has been made in optimizing molecular structures to improve the PCE. However, innovative material design strategies specifically aimed at enhancing PCE are still needed. Here, we have designed BDTS-2DPP-based molecules and propose a molecular design approach to develop donor materials that can significantly improve the PCE of OSCs. Density functional theory (DFT) and time-dependent DFT (TD-DFT) methods have been adopted in both gas and solvent phases. Our newly designed molecule M1 shows the highest absorption value (λ max = 846 nm), highest electron reorganization energy (λ e = 0.18 eV), and the lowest energy gap (E g = 1.81 eV) among all the designed molecules. M1 molecule also exhibits the highest dipole moment in both gas (10.62 D) and solvent phase (13.62 D), and their ground and excited state dipole moment difference is also higher (μ e - μ g = 2.99 D), which enhances its separation to make it a suitable candidate for charge transfer between HOMO-LUMO (97%). Newly designed molecule M3 is observed to have the highest voltage when the current is zero (V oc = 1.15 V) highest PCE value (21.90%) and highest fill factor (FF) value (89.42%). The lowest excitation binding energy is estimated by newly designed molecule M2 (E b = 0.30 eV), which indicates a higher rate of dissociation during the excitation as observed in transition density matrix (TDM) plots. Utilizing electron density difference maps, the newly designed molecules in dichloromethane solvent exhibited consistent intramolecular charge transfer (ICT). The designed molecules were evaluated against reference molecule R to determine if they exhibit superior optoelectronic capabilities. It is found that all designed molecules (M1-M5) exhibit reduced band gaps, are red-shifted in wavelength in comparison to a reference molecule R, and have remarkable charge motilities in terms of reorganisation energies.

Photoinduced charge transfer in small-molecule organic solar cells dependent on external electric field

In this paper, MTDATA is selected as the electron donor and BPhen as the acceptor. The trianiline structure of the donor molecule provides a variety of charge transfer pathways for charge separation. Based on Marcus theory, the photoinduced charge transfer properties of non-fullerene acceptor organic solar cells (NFA-OSCs) in external electric field (Fext) were studied. By analyzing the changes of reorganization energy (λ), Gibbs free energy (ΔG), electron transfer integral (Vda) and charge transfer rate under the influence of Fext, it was found that Fext can effectively regulate the charge transfer. Moreover, the change of charge transfer rate under Fext is similar to Vda, indicating that Vda is the main factor affecting charge transfer rate. To a certain extent, this study provides theoretical support for improving the photoelectric performance of NFA-OSCs.

Impact of Different π-Bridges on the Photovoltaic Performance of A-D-D'-D-A Small Molecule-Based Donors.

Three small donor molecule materials (S1, S2, S3) based on dithiophene [2,3-d:2',3'-d']dithiophene [1,2-b:4,5-b']dithiophene (DTBDT) utilized in this study were synthesized using the Vilsmeier-Haack reaction, traditional Stille coupling, and Knoevenagel condensation. Then, a variety of characterization methods were applied to study the differences in optical properties and photovoltaic devices among the three. By synthesizing S2 using a thiophene π-bridge based on S1, the blue shift in ultraviolet absorption can be enhanced, the band gap and energy level can be reduced, the open circuit voltage (VOC) can be increased to 0.75 V using the S2:Y6 device, and a power conversion efficiency (PCE) of 3% can be achieved. Also, after developing the device using Y6, S3 introduced the alkyl chain of thiophene π-bridge to S2, which improved the solubility of tiny donor molecules, achieved the maximum short-circuit current (JSC = 10.59 mA/cm2), filling factor (FF = 49.72%), and PCE (4.25%). Thus, a viable option for future design and synthesis of small donor molecule materials is to incorporate thiophene π-bridges into these materials, along with alkyl chains, in order to enhance the device's morphology and charge transfer behavior.

First Main‐Group Element Lewis Acid Thionyl Chloride Adduct and its Chemistry

AbstractAlthough the adduct of aluminum trichloride with thionyl chloride has been reported, no thionyl chloride adduct of a main group element Lewis acid or organometallic compound has been structurally characterized. In this communication we present the synthesis and reactivity of the structurally ascertained adduct of thionyl chloride with tris(pentafluoroethyl)gallane as a representative of a main group element Lewis acid. Gallium and indium compounds with electron withdrawing groups, e.g. the pentafluoroethyl ligand, display versatile properties. While gallates and indates, [MR4]−, behave as weakly coordinating anions, neutral gallanes and indanes, MR3, are strong Lewis acids. Salts with the tetrakis(pentafluoroethyl)gallate and ‐indate, [M(C2F5)4]− (M=Ga, In), have recently been studied in detail. In contrast to this, work on the syntheses of the free Lewis superacids M(C2F5)3 (M=Ga, In) is scarce and underdeveloped. The hydrates [M(C2F5)3(OH2)2] proved to be suitable starting materials, particularly due to their thermal stability. Herein we report on synthesis and characterization of reactive adducts, [M(C2F5)3D], with the weak donor molecules (D) SOCl2 and Me3SiF. The effective Lewis acidities of Ga(C2F5)3 and In(C2F5)3 were experimentally determined by the (modified) Gutmann‐Beckett method and their catalytic potential is showcased.

Frenkel and Charge‐Transfer Excitonic Couplings Strengthened by Thiophene‐Type Solvent Enables Binary Organic Solar Cells with 19.8 % Efficiency

AbstractOvercoming the trade‐off between short‐circuited current (Jsc) and open‐circuited voltage (Voc) is important to achieving high‐efficiency organic solar cells (OSCs). Previous works modulated the energy gap between Frenkel local exciton (LE) and charge‐transfer (CT) exciton, which served as the driving force of exciton splitting. Differently, our current work focuses on the modulation of LE‐CT excitonic coupling (tLE‐CT) via a simple but effective strategy that the 2‐chlorothiophene (2Cl−Th) solvent utilizes in the treatment of OSC active‐layer films. The results of our experimental measurements and theoretical simulations demonstrated that 2Cl−Th solvent initiates tighter intermolecular interactions with non‐fullerene acceptor in comparison with that of traditional chlorobenzene solvent, thus suppressing the acceptor's over‐aggregation and retarding the acceptor crystallization with reduced trap. Critically, the resulting shorter distances between donor and acceptor molecules in the 2Cl−Th treated blend efficiently strengthen tLE‐CT, which not only promotes exciton splitting but also reduces non‐radiative recombination. The champion efficiencies of 19.8 % (small‐area) with superior operational reliability (T80: 586 hours) and 17.0 % (large‐area) were yielded in 2Cl−Th treated cells. This work provided a new insight into modulating the exciton dynamics to overcome the trade‐off between Jsc and Voc, which can productively promote the development of the OSC field.

Frenkel and Charge-Transfer Excitonic Couplings Strengthened by Thiophene-Type Solvent Enables Binary Organic Solar Cells with 19.8 % Efficiency.

Overcoming the trade-off between short-circuited current (Jsc) and open-circuited voltage (Voc) is important to achieving high-efficiency organic solar cells (OSCs). Previous works modulated the energy gap between Frenkel local exciton (LE) and charge-transfer (CT) exciton, which served as the driving force of exciton splitting. Differently, our current work focuses on the modulation of LE-CT excitonic coupling (tLE-CT) via a simple but effective strategy that the 2-chlorothiophene (2Cl-Th) solvent utilizes in the treatment of OSC active-layer films. The results of our experimental measurements and theoretical simulations demonstrated that 2Cl-Th solvent initiates tighter intermolecular interactions with non-fullerene acceptor in comparison with that of traditional chlorobenzene solvent, thus suppressing the acceptor's over-aggregation and retarding the acceptor crystallization with reduced trap. Critically, the resulting shorter distances between donor and acceptor molecules in the 2Cl-Th treated blend efficiently strengthen tLE-CT, which not only promotes exciton splitting but also reduces non-radiative recombination. The champion efficiencies of 19.8 % (small-area) with superior operational reliability (T80: 586 hours) and 17.0 % (large-area) were yielded in 2Cl-Th treated cells. This work provided a new insight into modulating the exciton dynamics to overcome the trade-off between Jsc and Voc, which can productively promote the development of the OSC field.