Intermolecular Research Articles

Insights Into Janus Interfaces with Ordered Micro/Nanostructures for Low‐Temperature Differential Evaporation

AbstractLow‐temperature differential evaporation constitutes a promising direction for energy‐saving desalination. Herein, a novel Janus interfacial structure with well‐ordered micro/nanopores is developed. Fabricated Janus interfacial structure can weak the water intermolecular forces and pump water to the hydrophilic–hydrophobic junction. Within well‐ordered nanochannels, the increased curvature of the meniscus increases the ratio of thin water layers, thereby enhancing microscale heat transfer at the heated walls; in addition, the smaller nanopores limit the development of microscale vortices at the liquid–gas interface and prevent back mixing of intermediate water at the interface, which possess the nanoscale effect on intensifying the interfacial evaporation. These effects are validated by theoretical and experimental studies. Optimized Janus (20 nm)95°/25° structure exhibits evaporation fluxes up to 2.4 kg m−2 h−1 at 45 °C (feed side)/25 °C (permeate side, ambient pressure), as the theoretical evaporation enthalpy is only 30% of that for direct evaporation. The unique Janus structure simultaneously inhibits salt accumulation and achieve self‐cleaning, thereby maintaining steady performance during 480 h of continuous desalination and 50 cycles of batch operation. This work highlights a promising structural design strategy for separation materials with specific micro/nanoscopic topologies to achieve high performance thermally driven desalination applications.

Density Functional Theory Calculations for Interpretation of Infra-Red Spectra of Liquid Crystalline Chiral Compound

The experimental IR spectra of (S)-4′-(1-methylheptyloxycarbonyl) biphenyl-4-yl 4-[2-(2,2,3,3,4,4,4-heptafluorobutoxy) ethyl-1-oxy]-2-fluorobenzoate in the crystal phase are analyzed with the help of dispersion-corrected density functional theory (DFT+D3) calculations for isolated molecular monomer and dimer models, and a periodic model computed at the extended density functional tight-binding (xTB) level of theory. It is found that the frequency scaling coefficients obtained with the results of the molecular calculations are good matches for the crystal phase, being close to 1. The molecular and periodic models both confirm that varied intra- and intermolecular interactions are crucial in order to reproduce the broadened shape of the experimental band related to C=O stretching; the key factors are the conjugation of the ester groups with the aromatic rings and the varied intermolecular chemical environments, wherein the C=O group that bridges the biphenyl and F-substituted phenyl groups seems particularly sensitive. The C=O stretching vibrations are investigated as a function of temperature, covering the range of the crystal, smectic CA*, smectic C* and isotropic liquid phases. The structure changes are followed based on the X-ray diffraction patterns collected in the same temperatures as the IR spectra. The experimental and computational results taken together indicate that the amount of weak C=O…H-C hydrogen bonds between the molecules in the smectic layers decreases with increasing temperature.

Complexes of Zinc-Coordinated Heteroaromatic N-Oxides with Pyrene: Lewis Acid Effects on the Multicenter Donor–Acceptor Bonding

4-Nitroquinoline-N-oxide (NQO) and 4-nitropyridine-N-oxide (NPO) are important precursors for the synthesis of substituted heterocycles while NQO is a popular model mutagen and carcinogen broadly used in cancer research; intermolecular interactions are critical for their reactions or functioning in vivo. Herein, the effects of the coordination of N-oxide’s oxygen atom to Lewis acids on multicenter donor–acceptor bonding were explored via a combination of experimental and computational studies of the complexes of NQO and NPO with a typical π-electron donor, pyrene. Coordination with ZnCl2 increased the positive electrostatic potentials on the surfaces of these π-acceptors and lowered the energy of their LUMO. Analogous effects were observed upon the protonation of the N-oxides’ oxygen or bonding with boron trifluoride. The interaction of ZnCl2, NPO, or NQO and pyrene resulted in the formation of dark co-crystals comprising π-stacked Zn-coordinated N-oxides and pyrene similar to that found with protonated or (reported earlier) BF3-bonded N-oxides. Computational studies indicated that the coordination of N-oxides to zinc(II), BF3, or protonation led to the strengthening of the multicenter bonding of the nitro-heterocycle with pyrene, and this effect was related both to the increased electrostatic attraction and molecular–orbital interactions in their complexes.

Designing multi-epitope vaccine against human cytomegalovirus integrating pan-genome and reverse vaccinology pipelines

Human cytomegalovirus (HCMV) is accountable for high morbidity in neonates and immunosuppressed individuals. Due to the high genetic variability of HCMV, current prophylactic measures are insufficient. In this study, we employed a pan-genome and reverse vaccinology approach to screen the target for efficient vaccine candidates. Four proteins, envelope glycoprotein M, UL41A, US23, and US28, were shortlisted based on cellular localization, high solubility, antigenicity, and immunogenicity. A total of 29 B-cell and 44 T-cell highly immunogenic and antigenic epitopes with high global population coverage were finalized using immunoinformatics tools and algorithms. Further, the epitopes that were overlapping among the finalized B-cell and T-cell epitopes were linked with suitable linkers to form various combinations of multi-epitopic vaccine constructs. Among 16 vaccine constructs, Vc12 was selected based on physicochemical and structural properties. The docking and molecular simulations of VC12 were performed, which showed its high binding affinity (−23.35 kcal/mol) towards TLR4 due to intermolecular hydrogen bonds, salt bridges, and hydrophobic interactions, and there were only minimal fluctuations. Furthermore, Vc12 eliciting a good response was checked for its expression in Escherichia coli through in silico cloning and codon optimization, suggesting it to be a potent vaccine candidate.

Chemistry of Cyclo[18]Carbon (C18): A Review.

Carbon-based allotropes are propelling a technological revolution in communication, sensing, and computing, concurrently challenging fundamental theories of the previous century. Nevertheless, the demand for advanced carbon-based materials remains substantial. The crux lies in the efficient and reliable engineering of novel carbon allotrope. Although C18 has undergone theoretical and experimental investigation for an extended period, its preparation and direct observation in the condensed phase occurred only recently through STM/AFM techniques. The distinctive cyclic ring structure and the dual 18-center π delocalization character introduce various uncommon properties to C18, rendering it a subject worthy of in-depth exploration. In this context, this review delves into past developments contributing to the state-of-the-art understanding of C18 and provides insights into how future endeavours can expedite practical applications. Encompassing a broad spectrum, this review comprehensively investigates almost all facets of C18, including geometric characteristics, electron delocalization, bonding nature, aromaticity, reactivity, electronic excitation, UV/Vis spectrum, intermolecular interaction, response to external fields, electron affinity, ionization, and other molecular properties. Moreover, the review also outlines representative strategies for the direct synthesis and characterization of C18 using atom manipulation techniques. Following this, C18-based complexes are summarized, and potential applications in catalysis, electrochemical devices, optoelectronics, and sensing are discussed.

Photoluminescence Enhancement of 0D Organic-Inorganic Metal Halides via Aggregation-Induced Emission and Halide Substitution.

0D organic-inorganic metal halides (OIMHs) provide unprecedented versatility in structures and photoluminescence properties. Here, a series of bluish-white emissive 0D OIMHs, (TPE-TPP)2Sb2BrxCl8-x (x = 1.16 to 8), are prepared by assembling the 1-triphenylphosphonium-4-(1,2,2-triphenylethenyl)benzene cation (TPE-TPP)+ with antimony halides anions. Based on experimental characterizations and theoretical calculations, the emission of the 0D OIMHs are attributed to the fluorescence of the organic cations with aggregation-induced emission (AIE) properties. The 0D structure minimized the molecular motion and intermolecular interactions between (TPE-TPP)+ cations, effectively suppressing the non-radiative recombination processes. Consequently, the photoluminescence quantum efficiency (PLQE) of (TPE-TPP)2Sb2Br1.16Cl6.84 is significantly enhanced to 55.4% as compared to the organic salt (TPE-TPP)Br (20.5%). The PLQE of (TPE-TPP)2Sb2BrxCl8-x can also be readily manipulated by halide substitution, due to the competitive processes between non-radiative recombination on the inorganic moiety and the energy transfer from inorganic to organic. In addition, electrically driven light-emitting diodes (LEDs) are fabricated based on (TPE-TPP)2Sb2Br1.16Cl6.84 emitter, which exhibited bluish-white emission with a maximum external quantum efficiency (EQE) of 1.1% and luminance of 335cdm-2. This is the first report of electrically driven LED based on 0D OIMH with bluish-white emission.

Energetic Information from Information-Theoretic Approach in Density Functional Theory as Quantitative Measures of Physicochemical Properties.

The Hohenberg-Kohn theorem of density functional theory (DFT) stipulates that energy is a universal functional of electron density in the ground state, so energy can be thought of having encoded essential information for the density. Based on this, we recently proposed to quantify energetic information within the framework of information-theoretic approach (ITA) of DFT (J. Chem. Phys. 2022, 157, 101103). In this study, we systematically apply energetic information to a variety of chemical phenomena to validate the use of energetic information as quantitative measures of physicochemical properties. To that end, we employed six ITA quantities such as Shannon entropy and Fisher information for five energetic densities, yielding twenty-six viable energetic information quantities. Then, they are applied to correlate with physicochemical properties of molecular systems, including chemical bonding, conformational stability, intermolecular interactions, acidity, aromaticity, cooperativity, electrophilicity, nucleophilicity, and reactivity. Our results show that different quantities of energetic information often behave differently for different properties but a few of them, such as Shannon entropy of the total kinetic energy density and information gain of the Pauli energy density, stand out and strongly correlate with several properties across different categories of molecular systems. These results suggest that they can be employed as quantitative measures of physicochemical properties. This work not only enriches the body of our knowledge about the relationship between energy and information, but also provides scores of newly introduced explicit density functionals to quantify physicochemical properties, which can serve as robust features for building machine learning models in future studies.

Functionalizing Surfaces by Physical Vapor Deposition To Measure the Degree of Nanoscale Contact Using FRET.

Adhesion between solid materials is caused by intermolecular forces that only take place if the adhering surfaces are at nanoscale contact (NSC) (i.e., 0.1-0.4 nm. To study adhesion, NSC can be evaluated with Förster Resonance Energy Transfer (FRET). FRET uses the interaction of compatible fluorescence molecules to measure the nanometer distance between bonded surfaces. For this, each surface is labeled with one fluorescence dye, named the Donor or Acceptor. If these molecules are in NSC, a nonradiative Donor-Acceptor energy transfer will occur and can be detected using FRET spectroscopy. Here, for the first time, we introduce an innovative concept of a FRET-based NSC measurement employing dye-nanolayer films prepared by a physical vapor deposition (PVD). The dye nanolayers were prepared by PVD from the vaporization of the Donor and Acceptor molecules separately. The selected molecules, 7-Amino-4-methyl-cumarin (C120) and 5(6)-Carboxy-2',7'-dichlor-fluorescein (CDCF), present high quantum yields (QY, QYD = 0.91 and QYA = 0.64) and a low FRET distance range of 0.6-2.2 nm, adequate for the study of NSC. The produced dye-nanolayer films exhibit a uniform dye distribution (verified by atomic force microscopy) and suitable fluorescence intensities. To validate the NSC measurements, FRET spectroscopy experiments were performed with bonded dye-nanolayer films prepared under different loads (from 1.5 to 140 bar), thus creating different degrees of NSC. The results show an increase in FRET intensity (R 2 = 0.95) with the respective adhesion energy between the films, which is directly related to the degree of NSC. Hence, this work establishes FRET as an experimental technique for the measurement of NSC, and its relation to surface adhesion. Additionally, thanks to the FRET dye-nanolayer approach, the method can be employed on arbitrary surfaces. Essentially, any sufficiently transparent substrate can be functionalized with FRET compatible dyes to evaluate NSC, which represents a breakthrough in contact mechanics investigations of soft and hard solid materials.

Glass transition temperature as a unified parameter to design self-healable elastomers.

Self-healing ability of materials, particularly polymers, improves their functional stabilities and lifespan. To date, the designs for self-healable polymers have relied on specific intermolecular interactions or chemistries. We report a design methodology for self-healable polymers based on glass transition. Statistical copolymer series of two monomers with different glass transition temperatures (Tg) were synthesized, and their self-healing tendency depends on the Tg of the copolymers and the constituents. Self-healing occurs more efficiently when the difference in Tg between two monomer units is larger, within a narrow Tg range of the copolymers, irrespective of their functional groups. The self-healable copolymers are elastomeric and nonpolar. The strategy to graft glass transition onto self-healing would expand the scope of polymer design.

Design, synthesis, and anti-mycobacterial evaluation of 1,8-naphthyridine-3-carbonitrile analogues.

Twenty-eight compounds, viz., 1,8-naphthyridine-3-carbonitrile (ANC and ANA) derivatives, were designed and synthesized through a molecular hybridization approach. The structures of these compounds were analyzed and confirmed using 1H NMR, 13C NMR, LCMS, and elemental analyses. The synthesized compounds were evaluated by in vitro testing for their effectiveness against tuberculosis using the MABA assay, targeting the Mycobacterium tuberculosis H37Rv strain. Their minimum inhibitory concentration (MIC) was determined, showing that the tested compounds' MIC values ranged from 6.25 to ≤50 μg mL-1. Among the derivatives studied, ANA-12 demonstrated prominent anti-tuberculosis activity with a MIC of 6.25 μg mL-1. Compounds ANC-2, ANA-1, ANA 6-8, and ANA-10 displayed moderate to good anti-tuberculosis activity with MIC values of 12.5 μg mL-1. Compounds with MIC ≤ 12.5 μg mL-1 were screened against human embryonic kidney cells to assess their potential cytotoxicity. Interestingly, these compounds showed less toxicity towards normal cells, with a selectivity index value ≥ 11. To further evaluate the binding pattern in the active site of enoyl-ACP reductase (InhA) from Mtb (PDB-4TZK), a molecular docking analysis of compound ANA-12 was performed using the glide module of Schrodinger software. The stability, confirmation, and intermolecular interactions of the cocrystal ligand and the highly active compound ANA-12 on the chosen target protein were investigated through molecular dynamics simulations lasting 100 ns. In silico predictions were utilized to assess the ADMET properties of the final compounds. A suitable single crystal was developed and analyzed for compound ANA-5 to gain a deeper understanding of the compounds' structures.

Glass transition temperature as a unified parameter to design self-healable elastomers.

Self-healing ability of materials, particularly polymers, improves their functional stabilities and lifespan. To date, the designs for self-healable polymers have relied on specific intermolecular interactions or chemistries. We report a design methodology for self-healable polymers based on glass transition. Statistical copolymer series of two monomers with different glass transition temperatures (Tg) were synthesized, and their self-healing tendency depends on the Tg of the copolymers and the constituents. Self-healing occurs more efficiently when the difference in Tg between two monomer units is larger, within a narrow Tg range of the copolymers, irrespective of their functional groups. The self-healable copolymers are elastomeric and nonpolar. The strategy to graft glass transition onto self-healing would expand the scope of polymer design.

Computational Study of Molecular Interactions in ZnCl2(urea)2 Crystals as Precursors for Deep Eutectic Solvents

Deep eutectic solvents (DESs) are now enjoying an increased scientific interest due to their interesting properties and growing range of possible applications. Computational methods are at the forefront of deciphering their structure and dynamics. Type IV DESs, composed of metal chloride and a hydrogen bond donor, are among the less studied systems when it comes to their understanding at a molecular level. An important example of such systems is the zinc chloride–urea DES, already used in chemical synthesis, among others. In this paper, the ZnCl2(urea)2 crystal is studied from the point of view of its structure, infrared spectrum, and intermolecular interactions using periodic density functional theory and non-covalent interactions analysis. The two main structural motifs found in the crystal are a strongly hydrogen-bonded urea dimer assisted by chloride anions and a tetrahedral Zn(II) coordination complex. The crystal is composed of two interlocking parallel planes connected via the zinc cations. The infrared spectrum and bond lengths suggest a partially covalent character of the Zn−Cl bonds. The present analysis has far-reaching implications for the liquid ZnCl2–urea DES, explaining its fluidity, expected microstructure, and low conductivity, among others.

Adsorption of Flavonoids in a Transcriptional Regulator TtgR: Relative Binding Free Energies and Intermolecular Interactions.

Antimicrobial resistance in bacteria often arises from their ability to actively identify and expel toxic compounds. The bacterium strain Pseudomonas putida DOT-T1E utilizes its TtgABC efflux pump to confer robust resistance against antibiotics, flavonoids, and organic solvents. This resistance mechanism is intricately regulated at the transcriptional level by the TtgR protein. Through molecular dynamics and alchemical free energy simulations, we systematically examine the binding of seven flavonoids and their derivatives with the TtgR transcriptional regulator. Our simulations reveal distinct binding geometries and free energies for the flavonoids in the active site of the protein, which are driven by a range of noncovalent forces encompassing van der Waals, electrostatic, and hydrogen bonding interactions. The interplay of molecular structures, substituent patterns, and intermolecular interactions effectively stabilizes the bound flavonoids, confining their movements within the TtgR binding pocket. These findings yield valuable insights into the molecular determinants that govern ligand recognition in TtgR and shed light on the mechanism of antimicrobial resistance in P. putida DOT-T1E.

Thermo physical and spectroscopic properties of binary liquid mixtures at various temperatures and correlation with the Jouyban–Acree model (propargyl alcohol, ethanoic acid, propanoic acid and butanoic acid)

ABSTRACT A thorough investigation into binary mixtures of propargyl alcohol and various carboxylic acids (ethanoic, propanoic and butanoic) was conducted. Measurements of density (ρ), speed of sound (u) and viscosity (η) were meticulously performed across the entire range of mole fractions at temperatures (303.15 K−313.15 K) and atmospheric pressure (0.1 MPa). These data were used to calculate key thermodynamic and transport properties, including excess molar volume, excess isentropic compressibility, deviation in viscosity and excess Gibbs free energy of activation for viscous flow. The partial molar properties and infinite dilution molar partial properties were also determined for each binary system. Trends and behaviours were interpreted within the framework of intermolecular interactions, focusing on complex formation and specific chemical forces. The PFP theory and Jouyban–Acree model were critically applied, with confidence in the findings supported by FTIR studies.

Thiophene structured additives toward enhanced structural order and reduced non-radiative loss for 19.9 % efficiency organic solar cells

Organic semiconductors usually exhibit low structural-order owing to their weak intermolecular interactions, which leads to inferior charge transport and strong carrier recombination in photovoltaics. In this work, three thiophene structured solid additives namely thieno[3,2-b]thiophene (TT), 3,6-dibromothieno[3,2-b]thiophene (TTBB) and 3-bromo-6-iodio-thieno[3,2-b]thiophene (TTBI) are utilized to enhance the molecular interactions in a range of electron donors and acceptors. X-ray technique and molecular dynamics simulations reveal that by adjusting their electrostatic potential and dipole moment, their interacting site and interaction energy with donor (PM6 and D18) or acceptor (L8-BO) can be finely tuned. We find the most electropositive TTBB shows the strongest interaction with PM6, leading to enhanced crystallization; whilst the asymmetric TTBI brings the strongest molecular packing of L8-BO, consequent to more compact π-π stacking and ordered alkyl chain packing. As the results, the bulk heterojunction PM6:L8-BO photovoltaics upon the assistance of TTBI or TTBB obtain improved charge transport and reduced non-radiative energy loss, translating to power conversion efficiency (PCE) values of 18.7 % and 19.1 %. When further taking the synergetic effect of TTBB and TTBI on PM6(D18) and L8-BO respectively, the layer-by-layer deposited PM6(TTBB)/L8-BO(TTBI) and D18(TTBB)/L8-BO(TTBI) allowed superior PCEs of 19.4 % and 19.9 %, which are among the highest values of single-junction organic solar cells.

Quantum Mechanics Characterization of Non-Covalent Interaction in Nucleotide Fragments

Accurate calculation of non-covalent interaction energies in nucleotides is crucial for understanding the driving forces governing nucleic acid structure and function, as well as developing advanced molecular mechanics forcefields or machine learning potentials tailored to nucleic acids. Here, we dissect the nucleotides’ structure into three main constituents: nucleobases (A, G, C, T, and U), sugar moieties (ribose and deoxyribose), and phosphate group. The interactions among these fragments and between fragments and water were analyzed. Different quantum mechanical methods were compared for their accuracy in capturing the interaction energy. The non-covalent interaction energy was decomposed into electrostatics, exchange-repulsion, dispersion, and induction using two ab initio methods: Symmetry-Adapted Perturbation Theory (SAPT) and Absolutely Localized Molecular Orbitals (ALMO). These calculations provide a benchmark for different QM methods, in addition to providing a valuable understanding of the roles of various intermolecular forces in hydrogen bonding and aromatic stacking. With SAPT, a higher theory level and/or larger basis set did not necessarily give more accuracy. It is hard to know which combination would be best for a given system. In contrast, ALMO EDA2 did not show dependence on theory level or basis set; additionally, it is faster.

Synthesis of Technetium Carboxylates: Wheel-Like Octanuclear Clusters (Tc8(μ-O)8(RCOO)16, Where R = CF3, C6H5)─Potential Nanobuilding Units for Tc-MOFs.

Herein, we studied the behavior of TcO4- in trifluoroacetic anhydride (TFAA) under visible light irradiation in situ by UV-vis spectroscopy. One carboxylate of Tc(VII) C2F3O5Tc (1) and two wheel-like carboxylate clusters of Tc(IV) Tc8(μ-O)8(CF3COO)16 (2, 3) and Tc8(μ-O)8(C6H5COO)16 (4) were synthesized and analyzed using pXRD, TGA, UV-vis spectroscopy, and SCXRD techniques. According to SCXRD, it was found that Tc(IV) trifluoroacetate exists in two crystalline modifications. By UV-vis spectroscopy and DFT calculations, it was shown that the primary compound in the reaction system is trifluoroacetate Tc(VII). A technetium trifluoroacetate(VII) and Tc intermediates of unidentified nature both show photosensitivity. The influence of intermolecular noncovalent interactions on the volatility of trifluoroacetate and benzoate Tc(IV) is shown. The main regularities of chemical transformations of technetium in nonaqueous solutions of carboxylates have been revealed. The obtained data on the kinetics of the process suggest that technetium in trifluoroacetic anhydride can simultaneously exist in the form of Tc(VII), Tc(VI), Tc(V), and Tc(IV). Under laser ionization or prolonged heating, the formation of the Tc(II,III)-cluster is observed.

Repurposing the Open Global Health Library for the discovery of novel Mpro destabilizers with scope as broad-spectrum antivirals

The SARS coronavirus 2 (SARS-CoV-2) epidemic remains globally active. The emergence of new variants of interest and variants of concern (VoCs), which are potentially more vaccine-resistant and less sensitive to existing treatments, is evident due to their high prevalence. The prospective spread of such variants and other coronaviruses with epidemic potential demands preparedness that can be met by developing fast-track workflows to find new candidates that target viral proteins with a clear in vitro and in vivo phenotype. Mpro (or 3CLpro) is directly involved in the viral replication cycle and the production and function of viral polyproteins, which makes it an ideal target. The biological relevance of Mpro is highly conserved among betacoronaviruses like HCoV-OC43 and SARS-CoV-2, which makes the identification of new chemical scaffolds targeting them a good starting point for designing broad-spectrum antivirals. We report an optimized methodology based on orthogonal cell-free assays to identify small molecules that inhibit the binding pockets of both SARS-CoV-2-Mpro and HCoV-OC43-Mpro; this blockade correlates with antiviral activities in HCoV-OC43 cellular models. By using such a fast-tracking approach against the Open Global Health Library (Merck KGaA), we have found evidence of the antiviral activity of compound OGHL98. In silico studies dissecting intermolecular interactions between OGHL98 and both proteases and comprising docking and molecular dynamics simulations (MDSs) concluded that the binding mode was primarily governed by conserved H-bonds with their C-terminal amino acids and that the rational design of OGHL98 has potential against VoCs proteases resistant to current therapeutics.

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 energy gap between Frenkel local exciton (LE) and charge-transfer (CT) exciton, which is served as driving force of exciton splitting. Differently, our current work focuses on modulation of LE-CT excitonic coupling (tLE-CT) via a simple but effective strategy that the 2-chlorothiophene (2Cl-Th) solvent is utilized in treatment of OSC active-layer films. The results of our experimental measurements and theoretical simulations demonstrated that 2Cl-Th solvent initiates the 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. Importantly, the resulted shorter distances between donor and acceptor molecules in the 2Cl-Th treated blend efficiently strengthen tLE-CT, which not only promotes the exciton splitting but also reduces non-radiative recombination. The champion efficiencies of 19.8% (small-area) with a 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 OSC field.

A novel one-dimensional thiocyanate-bridged cobalt(III) complex: synthesis, crystal structure characterization and Hirshfeld surface analysis.

A new one-dimensional thiocyanate-bridged cobalt(III) Schiff base complex, namely, catena-poly[[[4-bromo-2-((Z)-{[2-(thiophen-2-yl)ethyl]imino}methyl)phenolato-κ2N,O]cobalt(III)]-μ-thiocyanato-κ2N:S], [Co(SCN)(C13H11BrNOS)2]n or [Co(μ1,3-SCN)L2]n (1), where HL is 4-bromo-2-((Z)-{[2-(thiophene-2-yl)ethyl]imino}methyl)phenol, a bidentate Schiff base prepared from the condensation reaction of 5-bromosalicylaldehyde and 2-(thiophen-2-yl)ethylamine, has been synthesized by stirring Co(ClO4)2·6H2O, the Schiff base HL and ammonium thiocyanate (in a 1:2:1 molar ratio) in ethanol medium. The complex was characterized by FT-IR, electronic spectra and single-crystal X-ray diffraction (SC-XRD) studies. The SC-XRD data suggest that the compound crystallizes in the orthorhombic space group Pca21. The CoIII ion in 1 adopts a distorted octahedral geometry, the metal sites being six-coordinated by one thiocyanate N atom and one thiocyanate S atom in apical positions, and by two imine N atoms and two phenolate O atoms from two anionic L- ligands which form the basal plane. The thiocyanate ligand acts as a μ-1,3 bridge, joining neighbouring CoIII atoms and forming a uniform zigzag one-dimensional polymeric chain. The crystallographic data were also used in the Hirshfeld surface (HS) analysis, which aimed to investigate the nature and quantitative significance of any noncovalent intermolecular interactions inside the crystal lattice. The crystal void parameters have also been computed and show the molecules to be tightly packed.