Molecular Packing Research Articles

Revealing crucial effects of reservoir environment and hydrocarbon fractions on fluid behaviour in kaolinite pores

The adsorption interactions of hydrocarbons and clay surfaces are crucial to understanding fluid behaviour within shale reservoirs and to mediating organic pollutants in soils. These interactions are affected by the diversity of complex hydrocarbon components and the variations in environmental conditions. This study examines the interactions between kaolinite clay, featuring two distinct basal surfaces, and an array of hydrocarbons. We assess the impact of various molecular structures, functional groups, and environmental conditions (focusing on the reservoir temperature and pressure ranges) on the adsorption selectivity, surface packing, molecular alignment and orientation, and diffusion of hydrocarbons. Analyses of molecular interaction energies provide a quantitative elucidation of the adsorption mechanisms of hydrocarbons on the different kaolinite surfaces. Our findings suggest that molecular configuration, functional group properties, and spatial effects dictate the distribution patterns of hydrocarbons for the different kaolinite surfaces. The differences in the interaction energy between various hydrocarbons with kaolinite reveal the adsorption strength of different hydrocarbons in the order of asphaltenes > heteroatomic hydrocarbons > saturated hydrocarbons > aromatic hydrocarbons. Furthermore, we observe that the adsorptive characteristics of hydrocarbons on kaolinite are highly temperature-sensitive, with increased temperatures markedly reducing the adsorption amount. Beyond a certain threshold, the effect of pressure rise on the fluid behaviour of hydrocarbons is non-negligible and is related to molecular packing and reduced mobility. Simulation results based on actual geological characteristics demonstrate notable adsorption disparities among hydrocarbon components on different kaolinite surfaces, influenced by competitive adsorption and clay surface interactions. Polar surfaces are predominantly occupied by heteroatomic hydrocarbons, whereas on non-polar surfaces, asphaltenes and heavy saturated hydrocarbons develop multi-layer adsorption structures, with molecules aligned parallel to the surface.

2,5-dichloro-3,4-diiodothiophene as a versatile solid additive for high-performance organic solar cells

Volatile solid additive (SA) with diverse chemical structures has been proved to be an alternative to prepare high-efficient organic solar cells (OSCs). While, various organic photovoltaic materials raise challenges in selecting suitable SAs during the device optimization. Herein, based on the simple and commonly used thiophene unit, we proposed a perhalogenated 2,5-dichloro-3,4-diiodothiophene (SA-T5) as the SA for the device optimizations. As results, the capacity of SA-T5 in optimizing molecular packings of small-molecular acceptor L8-BO, dimeric acceptor DL8, and polymeric acceptor PY-DT based blend films has been demonstated. Their optimized morphologies assisted by SA-T5 contribute to the suppressed charge recombination and enhanced charge transportation, resulting in their improved short-circuit current density and fill factor, simultaneously. In comparsion with as-cast devices, SA-T5-treated devices showed significantly improved power conversion efficiencies (PCEs) of 18.8 % for PM6:L8-BO, 17.8 % for PM6:DL8, and 17.6 % for PM6:PY-DT, respectively. Furthermore, the potential of SA-T5 in obtaining high-performance ternary OSCs was also confirmed, for example, a 18.1 % efficiency was realized in PM6:DL8:L8-BO based device. To our knowledge, the performance of these SA-T5-treated devices reaches the best results of different acceptor-based OSCs. Importantly, this work provides a rare and successful case to develop versatile SAs for high-performance OSCs.

Versatile Self‐Assembled Monolayer Material Enables Efficient Organic Photovoltaic Devices and Modules

AbstractEfficient and stable hole transport layer (HTL) is an important component of organic photovoltaics (OPV). Herein, a novel self‐assembled monolayer material of 4PADCB (short for (4‐(7H‐dibenzo[c,g]carbazol‐7‐yl)butyl)phosphonic acid) as HTL for non‐fullerene (NF) OPV is reported. Compared to the widely used PEDOT:PSS HTL, the usage of 4PADCB not only enhances photon incident and charge generation but also effectively improves the morphology of the upper active layer, promotes molecular packing, and balances the carrier transport within active layer. As a result, the single‐junction binary D18:L8BO OPV, employing 4PADCB as HTL, achieves a high‐power conversion efficiency (PCE) of 19.02% with excellent storage stability. Furthermore, a 19.3 cm2 OPV module comprising seven sub‐cells demonstrates a maximum PCE of 15.44%, which is the highest value of reported efficiency for large‐area binary OPV modules. Meanwhile, the module is the first demonstration of an OPV module based on self‐assembled monolayer material. This work underscores the substantial potential for the application of 4PADCB in efficient NF OPV devices and high‐throughput large‐area modules.

Structure, Self-Assembly, and Phase Behavior of Neuroactive N-Acyl GABAs: Doxorubicin Encapsulation in NPGABA/DPPC Liposomes and Release Studies.

N-Acylated amino acids and neurotransmitters in mammals exert significant biological effects on the nervous system, immune responses, and vasculature. N-Acyl derivatives of γ-aminobutyric acid (N-acyl GABA), which belong to both classes mentioned above, are prominent among them. In this work, a homologous series of N-acyl GABAs bearing saturated N-acyl chains (C8-C18) have been synthesized and characterized with respect to self-assembly, thermotropic phase behavior, and supramolecular organization. Differential scanning calorimetric studies revealed that the transition enthalpies and entropies of N-acyl GABAs are linearly dependent on the acyl chain length. The crystal structure of N-tridecanoyl GABA showed that the molecules are packed in bilayers with the acyl chains aligned parallel to the bilayer normal and that the carboxyl groups from opposite layers associate to form dimeric structures involving strong O-H···O hydrogen bonds. In addition, N-H···O and C-H···O hydrogen bonds between amide moieties of adjacent molecules within each layer stabilize the molecular packing. Powder X-ray diffraction studies showed odd-even alternation in the d spacings, suggesting that the odd chain and even chain compounds pack differently. Equimolar mixtures of N-palmitoyl GABA and dipalmitoylphosphatidylcholine (DPPC) were found to form stable unilamellar vesicles with diameters of ∼300-340 nm, which could encapsulate doxorubicin, an anticancer drug, with higher efficiency and better release characteristics than DPPC liposomes at physiologically relevant pH. These liposomes exhibit faster release of doxorubicin at acidic pH (<7.0), indicating their potential utility as drug carriers in cancer chemotherapy.

Convoluted micellar morphological transitions driven by tailorable mesogenic ordering effect from discotic mesogen-containing block copolymer

Solution-state self-assemblies of block copolymers to form nanostructures are tremendously attractive for their tailorable morphologies and functionalities. While incorporating moieties with strong ordering effects may introduce highly orientational control over the molecular packing and dictate assembly behaviors, subtle and delicate driving forces can yield slower kinetics to reveal manifold metastable morphologies. Herein, we report the unusually convoluted self-assembly behaviors of a liquid crystalline block copolymer bearing triphenylene discotic mesogens. They undergo unusual multiple morphological transitions spontaneously, driven by their intrinsic subtle liquid crystalline ordering effect. Meanwhile, liquid crystalline orderedness can also be built very quickly by doping the mesogens with small-molecule dopants, and the morphological transitions are dramatically accelerated and various exotic micelles are produced. Surprisingly, with high doping levels, the self-assembly mechanism of this block copolymer is completely changed from intramolecular chain shuffling and rearrangement to nucleation-growth mode, based on which self-seeding experiments can be conducted to produce highly uniform fibrils.

Self‐Adaptive Aromatic Cation‐π Driven Dimensional Polymorphism in Supramolecular Polymers for the Photocatalytic Oxidation and Separation of Aromatic/Cyclic Aliphatic Compounds

AbstractThe phenomenon of polymorphism is ubiquitous in nature, the controlled manipulation of which not only increases our ontological understanding of nature but also facilitates the conceptualization and realization of novel functional materials. However, achieving targeted polymorphism in supramolecular assemblies (SAs) remains a formidable challenge, largely because of the constraints inherent in controlling the specific binding motifs of noncovalent interactions. Herein, we propose self‐adaptive aromatic cation‐π binding motifs to construct polymorphic SAs in both the solid and solution states. Using distinct discrete cation‐π‐cation and long‐range cation‐π binding motifs enables control of the self‐assembly directionality of a C2h‐symmetric bifunctional monomer, resulting in the successful formation of both two‐dimensional and three‐dimensional crystalline SAs (2D‐CSA and 3D‐CSA). The differences in the molecular packing of 3D‐CSA compared with that of 2D‐CSA significantly improve the charge separation and carrier mobility, leading to enhanced photocatalytic activity for the aerobic oxidation of thioanisole to methyl phenyl sulfoxide (yield of 99 % vs 57 %). 2D‐CSA, which has a vertical extended structure with favorable stronger interaction with toluene though face‐to‐face cation‐π interactions than methylcyclohexane, shows higher toluene/methylcyclohexane separation efficiency than 3D‐CSA (96.9 % for 2D‐CSA vs 56.3 % for 3D‐CSA).

Self-Adaptive Aromatic Cation-π Driven Dimensional Polymorphism in Supramolecular Polymers for the Photocatalytic Oxidation and Separation of Aromatic/Cyclic Aliphatic Compounds.

The phenomenon of polymorphism is ubiquitous in nature, the controlled manipulation of which not only increases our ontological understanding of nature but also facilitates the conceptualization and realization of novel functional materials. However, achieving targeted polymorphism in supramolecular assemblies (SAs) remains a formidable challenge, largely because of the constraints inherent in controlling the specific binding motifs of noncovalent interactions. Herein, we propose self-adaptive aromatic cation-π binding motifs to construct polymorphic SAs in both the solid and solution states. Using distinct discrete cation-π-cation and long-range cation-π binding motifs enables control of the self-assembly directionality of a C2h-symmetric bifunctional monomer, resulting in the successful formation of both two-dimensional and three-dimensional crystalline SAs (2D-CSA and 3D-CSA). The differences in the molecular packing of 3D-CSA compared with that of 2D-CSA significantly improve the charge separation and carrier mobility, leading to enhanced photocatalytic activity for the aerobic oxidation of thioanisole to methyl phenyl sulfoxide (yield of 99 % vs 57 %). 2D-CSA, which has a vertical extended structure with favorable stronger interaction with toluene though face-to-face cation-π interactions than methylcyclohexane, shows higher toluene/methylcyclohexane separation efficiency than 3D-CSA (96.9 % for 2D-CSA vs 56.3 % for 3D-CSA).

Docosahexaenoic Acid Controls Pulmonary Macrophage Lipid Raft Size and Inflammation

BackgroundDocosahexaenoic acid (DHA) controls the biophysical organization of plasma membrane sphingolipid/cholesterol-enriched lipid rafts to exert anti-inflammatory effects, particularly in lymphocytes. However, the impact of DHA on the spatial arrangement of alveolar macrophage lipid rafts and inflammation is unknown. ObjectivesThe primary objective was to determine how DHA controls lipid raft organization and function of alveolar macrophages. As proof-of-concept, we also investigated DHA’s anti-inflammatory effects on select pulmonary inflammatory markers with a murine influenza model. MethodsMH-S cells, an alveolar macrophage line, were treated with 50 μM DHA or vehicle control and were used to study plasma membrane molecular organization with fluorescence-based methods. Biomimetic membranes and coarse grain molecular dynamic (MD) simulations were employed to investigate how DHA mechanistically controls lipid raft size. qRT-PCR, mass spectrometry, and ELISAs were used to quantify downstream inflammatory signaling transcripts, oxylipins, and cytokines, respectively. Lungs from DHA-fed influenza-infected mice were analyzed for specific inflammatory markers. ResultsDHA increased the size of lipid rafts while decreasing the molecular packing of the MH-S plasma membrane. Adding a DHA-containing phospholipid to a biomimetic lipid raft-containing membrane led to condensing, which was reversed with the removal of cholesterol. MD simulations revealed DHA nucleated lipid rafts by driving cholesterol and sphingomyelin into rafts. Downstream of the plasma membrane, DHA lowered the concentration of select inflammatory transcripts, oxylipins, and IL-6 secretion. DHA lowered pulmonary Il6 and Tnf-α mRNA expression and increased anti-inflammatory oxylipins of influenza-infected mice. ConclusionsThe data suggest a model in which the localization of DHA acyl chains to nonrafts is driving sphingomyelin and cholesterol molecules into larger lipid rafts, which may serve as a trigger to impede signaling and lower inflammation. These findings also identify alveolar macrophages as a target of DHA and underscore the anti-inflammatory properties of DHA for lung inflammation.

Tweaking the Non-Volatile Write-Once-Read-Many-Times (WORM) Memory using Donor-Acceptor Architecture with Isatin as Core Acceptor.

Organic memory devices have attracted attention because they promise flexible electronics, low manufacturing costs, and compatibility with large-scale integration. A series of new D-A architectures were synthesized employing different donor groups and the isatin moiety as the acceptor through Suzuki-Miyaura coupling reactions. Strong intramolecular interactions were observed in the synthesized compounds, further corroborated by an optimal bandgap. The SEM investigation confirmed good molecular ordering and superior thin film surface coverage. All the compounds demonstrated notable binary Write-Once-Read-Many-Times (WORM) memory behaviour. The threshold switching voltage for these D-A systems ranged from -0.79 to -2.37 V, with the compound having isobutyl substituent showing the lowest threshold voltage and maximum ON/OFF ratio of 102, thus outperforming others. The combined effects of charge transfer and charge trapping are responsible for the resistive switching mechanism prevailing in these systems. The alterations in D-A molecules that affect molecular packing, thin film morphology, and, finally, the memory performance of the active layer are highlighted in this work.

New thiazole derivatives: Synthesis, X-ray crystal structure, Hirshfeld surface analysis, and biological evaluations as potential antimicrobial and antitumor agents

Thiazole ring has a wide range of biological activities which is proven by its presence in more than eighteen FDA-approved drugs in addition to several compounds that are currently under clinical investigation. Substitution of the thiazole ring at positions 2,4, and 5 led to new derivatives with potent biological activities. Interestingly, the bromination of ethyl 2-cyano-2-(4-methyl-3-phenylthiazol-2(3H)-ylidene)acetate (1) in acetic acid afforded (Z)-ethyl 2-(5‑bromo-4-(bromomethyl)-3-phenylthiazol-2(3H)-ylidene)-2-cyanoacetate (2) instead of the expected bromomethyl derivative 3. The reaction of thiazole derivative 2 with p-anisidine or aniline produced the corresponding thiazole derivatives 5a,b. The synthesized compounds were characterized based on their spectral and elemental data. Moreover, the structure of compound 2 was determined through X-ray crystallography. The molecular structure of 2 was crystallized in the orthorhombic, Pna21, a = 15.8144 (6) Å, b= 9.0238 (4) Å, c = 11.3296 (4) Å, V = 1616.80 (11) Å3, Z = 4. Analysis of the dnorm map and fingerprint plot for all possible intermolecular interactions in the crystal structure of thiazole 2 indicated the importance of the Br…O, O…H, and Br…H interactions in the molecular packing. The O1…H14A (2.548 Å), Br1…O1 (3.211 Å) and Br2…H7B (2.931 Å) interactions are the most short contacts. In addition, the percentages of the Br…O, O…H, and Br…H contacts are 2.3, 10.3 and 22.1 %, respectively. The antimicrobial activity of thiazole derivative 5a was tested, and the results revealed that it is equipotent to both Ampicillin against Staphylococcus aureus and to Gentamycin against Salmonella SP. In comparison to Doxorubicin, thiazole 5a showed less antitumor activity against the hepatocellular carcinoma (HepG-2) and colon carcinoma (HCT-116) cell lines.

Balancing Solvent Polarity and Drying‐Kinetics for Processing Nonfullerene Acceptors Toward High‐Performance Organic Solar Cells

In recent years, the emergence of high‐efficiency nonfullerene acceptors (NFAs) has pushed the power conversion efficiency (PCE) beyond 19% in organic solar cells (OSCs). For solution processing of the photoactive layers, the study of solvent properties on device performance has become a hot research topic toward up‐scaling. Herein, the key roles of balancing solvent polarity and drying kinetics for processing of small molecular NFAs toward high‐performance OSCs are revealed. It is demonstrated that the synergistic effect of solvent polarity and drying kinetics significantly affects the multilength scale morphology of solid films and photovoltaic performance. Furthermore, the self‐assembly of NFAs in solution and the resulting thin film microstructures induced by electrostatic interactions with polarized additives are even more sensitive to solvent polarity and drying kinetics. Finally, the optimized devices achieve an outstanding PCE of 18.54% by fine‐tuning the microstructure with polar solvent and fast‐drying kinetics to form improved molecular packing and structure size. The work provides a novel view and deeper insights into the general selection rules of solvents toward the solution processing of high‐performance nonfullerene OSCs.

Advancing MR‐TADF OLED Toward True‐Blue CIE Value via Asymmetric Host Materials with Amorphous Morphology

AbstractThe new host materials are reported to boost the multiple resonance‐induced thermally activated delayed fluorescence (MR‐TADF) based pure deep‐blue organic light emitting diodes (OLEDs) toward further shortening the emission full width at the half maximum (FWHM). Based on an unusual asymmetric design concept, two new host compounds Bz2cb and Bz2cbz are synthesized. Despite possessing a compact and rigid molecular packing in crystal, Bz2cbz shows pure amorphous morphology via vapor deposition, as confirmed by the grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) analysis. Via incorporating a promising MR‐TADF emitter, ν‐DABNA‐O‐Me, into Bz2cb and Bz2cbz films, highly pure deep‐blue OLEDs are successfully demonstrated. Remarkably, the Bz2cbz device exhibits a 464 nm electroluminescence (EL) with narrow FWHM of 22 nm, accompanied by the reduction of the 0–1 vibronic sideband, and a maximum external quantum efficiency (EQEmax) of 28.2%, which, overall, reaches the true‐blue Commission Internationale de l'Eclairage coordinates (CIE) of (0.13, 0.07) and the high blue index of 253. The amorphous film formation turns out to be an important factor that is previously unrecognized to externally fine‐tune the MR‐TADF OLEDs toward even higher color purity.

Designing a Novel Wide Bandgap Small Molecule Guest for Enhanced Stability and Morphology Mediation in Ternary Organic Solar Cells with over 19.3% Efficiency.

In this study, a novel wide-bandgap small molecule guest material, ITOA, designed and synthesized for fabricating efficient ternary organic solar cells (OSCs) ITOA complements the absorbance of the PM6:Y6 binary system, exhibiting strong crystallinity and modest miscibility. ITOA optimizes the morphology by promoting intensive molecular packing, reducing domain size, and establishing a preferred vertical phase distribution. These features contribute to improved and well-balanced charge transport, suppressed carrier recombination, and efficient exciton dissociation. Consequently, a significantly enhanced efficiency of 18.62% for the ternary device is achieved, accompanied by increased short-circuit current density (JSC), fill factor (FF), and open-circuit voltage (VOC). Building on this success, replacing Y6 with BTP-eC9 leads to an outstanding PCE of 19.33% for the ternary OSCs. Notably, the introduction of ITOA expedites the formation of the optimized morphology, resulting in an impressive PCE of 18.04% for the ternary device without any postprocessing. Moreover, the ternary device exhibits enhanced operational stability under maximum power point (MPP) tracking. This comprehensive study demonstrates that a rationally designed guest molecule can optimize morphology, reduce energy loss, and streamline the fabrication process, essential for achieving high efficiency and stability in OSCs, paving the way for practical commercial applications.

Carbazol-benzothiadiazole based D–A–D mesogens: Self-assembly and photophysical characteristics

Three carbazole(C)-benzothiadiazole(B) based D-A-D mesogens CBC/n (n = 12, 16) and CTBTC/16 containing terminal N-trialkoxylbenzyl carbazoles at both side of central benzothiadiazole core have been designed and synthesized. By inserting thiophene (T) unit between B and C units, the rigid core was elongated and the molecular conformation changed from twist to planar one, thereby the liquid crystal (LC) phase changed from SmA to Col/hex phase. Such molecular packings caused by inserting T unit remained in their organogels formed in organic solvents. The long-core compound CTBTC/16 containing T unit with a more planar and tighter π-π packing structure showed a significant optical red shift and a stronger intramolecular charge transfer (ICT) effect than the short-core compounds CBC/n without thiophene unit. These compounds are all strong fluorescent in solution with fluorescence quantum yields (ΦF) ranging from 38 % to 86 %. But their solid fluorescence quantum yields (ΦFs) differ greatly with values of 43 %, 11 % and 0.6 % for CBC/12, CBC/16 and CTBTC/16 respectively. Further, short core compound CBC/12 with the highest ΦFs showed different ΦFs in its three different solid aggregation states. The application of the short twist core compound CBC/12 as white light-emitting diodes (LEDs) has been realized. The influence of the thiophene unit as well as the terminal alkyl chain length on self-assembly and ΦFs of these compounds is discussed.

Generic Behavior of Ultrastability and Anisotropic Molecular Packing in Codeposited Organic Semiconductor Glass Mixtures

Generic Behavior of Ultrastability and Anisotropic Molecular Packing in Codeposited Organic Semiconductor Glass Mixtures

Enhanced molecular planarity for high-performance photodetectors: Effect of backbone conformation via alkyl substitution position control in dithienoquinoxaline-based conjugated polymers

Conjugated polymers (CPs) with donor and acceptor units exhibit a flexible conformation due to the rotation of the single bond of the bridge groups which greatly hinders a precise study of their photodetection properties. Moreover, the modulation mechanism related to complex factors of CPs molecular conformation on photodetection performance is not clear, causing CP-based organic photodiodes (OPDs) to generally suffer from high dark current and low specific detectivity. In this work, we synthesized two novel PBQx-i-4F and PBQx-o-4F CPs by combining fluorinated BDT with DTQx units using i- and o-alkylated side chain-based thiophene linkages, respectively. Quantum simulation and photo-physics study revealed that PBQx-i-4F displayed a dominant trans conformation, a more planar molecule structure, and high utilization efficiency of photoinduced excitons. The OPDs based on PBQx-i-4F exhibited higher on–off ratios by over two orders of magnitude and higher detectivity (Dsh*) by nearly one order of magnitude compared with those based on PBQx-o-4F. PBQx-i-4F with the i-alkyl substitution on the thiophene linkage displayed enhanced planarity, resulting in more ordered packing and larger population of face-on orientation in film, where decreased trap density and trap-assisted recombination led to reduced dark current and improved charge transport. In summary, our work provides an insight into the relationship between the fine-tuning of the molecular conformation, planarity, and packing of CPs and their photodetection properties in OPDs.

Manipulation of the Self‐Assembly Morphology by Side‐Chain Engineering of Quinoxaline‐Substituted Organic Photothermal Molecules for Highly Efficient Solar‐Thermal Conversion and Applications

AbstractOrganic photothermal materials have attracted increasing attention because of their structural diversity, flexibility, and compatibility. However, their energy conversion efficiency is limited owing to the narrow absorption spectrum, strong reflection/transmittance, and insufficient nonradiative decay. In this study, two quinoxaline‐based D–A‐D–A‐D‐type molecules with ethyl (BQE) or carboxylate (BQC) substituents were synthesized. Strong intramolecular charge transfer provided both molecules with a broad absorption range of 350–1000 nm. In addition, the high reorganization energy and weak molecular packing of BQE resulted in efficient nonradiative decay. More importantly, the self‐assembly of BQE leads to a textured surface and enhances the light‐trapping efficiency with significantly reduced light reflection/transmittance. Consequently, BQE achieved an impressive solar‐thermal conversion efficiency of 18.16 % under 1.0 kW m−2 irradiation with good photobleaching resistance. Based on this knowledge, the water evaporation rate of 1.2 kg m−2 h−1 was attained for the BQE‐based interfacial evaporation device with an efficiency of 83 % under 1.0 kW m−2 simulated sunlight. Finally, the synergetic integration of solar‐steam and thermoelectric co‐generation devices based on BQE was realized without significantly sacrificing solar‐steam efficiency. This underscores the practical applications of BQE‐based technology in effectively harnessing photothermal energy. This study provides new insights into the molecular design for enhancing light‐trapping management by molecular self‐assembly, paving the way for photothermal‐driven applications of organic photothermal materials.

Manipulation of the Self-Assembly Morphology by Side-Chain Engineering of Quinoxaline-Substituted Organic Photothermal Molecules for Highly Efficient Solar-Thermal Conversion and Applications.

Organic photothermal materials have attracted increasing attention because of their structural diversity, flexibility, and compatibility. However, their energy conversion efficiency is limited owing to the narrow absorption spectrum, strong reflection/transmittance, and insufficient nonradiative decay. In this study, two quinoxaline-based D-A-D-A-D-type molecules with ethyl (BQE) or carboxylate (BQC) substituents were synthesized. Strong intramolecular charge transfer provided both molecules with a broad absorption range of 350-1000 nm. In addition, the high reorganization energy and weak molecular packing of BQE resulted in efficient nonradiative decay. More importantly, the self-assembly of BQE leads to a textured surface and enhances the light-trapping efficiency with significantly reduced light reflection/transmittance. Consequently, BQE achieved an impressive solar-thermal conversion efficiency of 18.16 % under 1.0 kW m-2 irradiation with good photobleaching resistance. Based on this knowledge, the water evaporation rate of 1.2 kg m-2 h-1 was attained for the BQE-based interfacial evaporation device with an efficiency of 83 % under 1.0 kW m-2 simulated sunlight. Finally, the synergetic integration of solar-steam and thermoelectric co-generation devices based on BQE was realized without significantly sacrificing solar-steam efficiency. This underscores the practical applications of BQE-based technology in effectively harnessing photothermal energy. This study provides new insights into the molecular design for enhancing light-trapping management by molecular self-assembly, paving the way for photothermal-driven applications of organic photothermal materials.

Crystal structure and Hirshfeld surface analysis of 8-benzyl-1-[(4-methyl-phen-yl)sulfon-yl]-2,7,8,9-tetra-hydro-1H-3,6:10,13-diep-oxy-1,8-benzodi-aza-cyclo-penta-decine ethanol hemisolvate.

The asymmetric unit of the title compound, 2C31H28N2O4S·C2H6O, contains a parent mol-ecule and a half mol-ecule of ethanol solvent. The main compound stabilizes its mol-ecular conformation by forming a ring with an R 1 2(7) motif with the ethanol solvent mol-ecule. In the crystal, mol-ecules are connected by C-H⋯O and O-H⋯O hydrogen bonds, forming a three-dimensional network. In addition, C-H⋯π inter-actions also strengthen the mol-ecular packing.

Crossbreeding Effect of Chalcogenation and Iodination on Benzene Additives Enables Optimized Morphology and 19.68% Efficiency of Organic Solar Cells.

Volatile solid additives have attracted increasing attention in optimizing the morphology and improving the performance of currently dominated non-fullerene acceptor-based organic solar cells (OSCs). However, the underlying principles governing the rational design of volatile solid additives remain elusive. Herein, a series of efficient volatile solid additives are successfully developed by the crossbreeding effect of chalcogenation and iodination for optimizing the morphology and improving the photovoltaic performances of OSCs. Five benzene derivatives of 1,4-dimethoxybenzene (DOB), 1-iodo-4-methoxybenzene (OIB), 1-iodo-4-methylthiobenzene (SIB), 1,4-dimethylthiobenzene (DSB) and 1,4-diiodobenzene (DIB) are systematically studied, where the widely used DIB is used as the reference. The effect of chalcogenation and iodination on the overall property is comprehensively investigated, which indicates that the versatile functional groups provided various types of noncovalent interactions with the host materials for modulating the morphology. Among them, SIB with the combination of sulphuration and iodination enabled more appropriate interactions with the host blend, giving rise to a highly ordered molecular packing and more favorable morphology. As a result, the binary OSCs based on PM6:L8-BO and PBTz-F:L8-BO as well as the ternary OSCs based on PBTz-F:PM6:L8-BO achieved impressive high PCEs of 18.87%, 18.81% and 19.68%, respectively, which are among the highest values for OSCs.