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Intermolecular interactions with polycyclic aromatic hydrocarbons (PAHs) represent an important area of physisorption studies. These investigations are often hampered by a size of interacting PAHs, which makes the calculation prohibitively expensive. Therefore, methods designed to deal with large molecules could be helpful to reduce the computational costs of such studies. Recently we have introduced a new systematic approach for the molecular fragmentation of PAHs, denoted as AROFRAG, which decomposes a large PAH molecule into a set of predefined small PAHs with a benzene ring being the smallest unbreakable unit, and which in conjunction with the Molecules‐in‐Molecules (MIM) approach provides an accurate description of total molecular energies. In this contribution we propose an extension of the AROFRAG, which provides a description of intermolecular interactions for complexes composed of PAH molecules. The examination of interaction energy partitioning for various test cases shows that the AROFRAG3 model connected with the MIM approach accurately reproduces all important components of the interaction energy. An additional important finding in our study is that the computationally expensive long‐range electron‐correlation part of the interaction energy, that is, the dispersion component, is well described at lower AROFRAG levels even without MIM, which makes the latter models interesting alternatives to existing methods for an accurate description of the electron‐correlated part of the interaction energy. [ABSTRACT FROM AUTHOR]

Biredox deep‐eutectic solvents (DESs)‐based electrolytes have shown unique features in non‐aqueous asymmetrical redox flow batteries (RFBs) that can potentially mitigate the crossover issue. However, strong intermolecular interactions among the electrolyte constituents in DESs bring in practical challenges such as limited mass transfer rates, slow redox kinetics, and degraded cyclability. Here, by using a novel biredox‐type DES based on 4‐methoxy‐2,2,6,6‐tetramethyl‐1‐piperidinyloxy (4‐MeO‐TEMPO) and 3,3′‐dimethylazobenzene (3,3′‐Azo) as a model electrolyte system, the intermolecular interaction involving in the biredox DESs is unlocked by first‐principles calculations, and their influence on the electrochemical performance of biredox DESs couples is systematically investigated in comprehensive consideration of the solvents and the supporting salts. It demonstrates that employing tetrabutylammonium bis‐trifluoromethane sulfonimidate‐acetonitrile as the supporting electrolyte synergistically weakens the intermolecular interactions within the DESs, thereby significantly promoting the redox kinetics and electrochemical reversibility in non‐aqueous symmetrical RBFs. With such an optimized electrolyte, a prototype symmetrical cell under static mode is capable of delivering a high output voltage of ∼2.15 V, a decent cyclability, and the exceptional rate capability with a current density of 25 mA cm−2. This study provides a simple yet effective way to develop advanced RFBs with dependable electrolyte regulation. [ABSTRACT FROM AUTHOR]

A new type of material, organic salts in the crystal and crystalline powder state, with both excitation wavelength dependent (Ex‐De) fluorescence and Ex‐De phosphorescence under ambient conditions have been reported. The single component triphenylsulfonium chloride displays tunable fluorescent colors ranging from light purple to sky blue and tunable afterglow colors varying from green to yellowish green, to yellow (lifetimes: 57, 141, 66 ms, afterglow lasting for 2.1, 2.0, 2.3 s). The relationship between the structure and luminescence performance of 17 sulfonium salt derivatives confirms the pivotal roles of both the anions and the electronic and steric effect of substituent factors for luminescence. Single‐crystal analysis reveals that unique ionic bonding and intermolecular interaction can promote an ordered arrangement of organic salts in a crystal state, which then can facilitate molecular aggregation for phosphorescence generation. Theoretical calculations have also confirmed this viewpoint. More importantly, these sulfonium salt derivatives can be used for advanced multimodal anti‐counterfeiting and mitochondrial imaging, respectively. This study has not only expanded the scope of Ex‐De materials but also extended their applications. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Designing electrolytes that are compatible with graphite anodes and possess flame‐retardant features is strongly demanded in potassium‐ion batteries (PIBs) to inhibit solvent co‐insertion and graphite exfoliation, and also stabilize the highly active potassium‐based species (e.g., KC8). Herein, a nonflammable electrolyte is designed by introducing the fluoroethers to stabilize graphite anodes, particularly at an ultralow concentration (<0.43 m) that is rarely reported before. It is discovered that intermolecular interactions can form between the 1,1,2,2‐tetrafluoroethyl‐2,2,3,3‐tetrafluoropropyl ether (i.e., HFE) diluent and trimethyl phosphate (TMP) flame‐retardant by electronegative fluorine (δ−F) and electropositive hydrogen (δ+H). The intermolecular interactions can change the potassium ion (K+) solvation structure (e.g., weakening the K+‐TMP interaction), and then determine the properties of the K+‐solvent‐anion complex at the electrode interface. a molecular interfacial model is presented with a new coordination mechanism involving the diluent to elucidate the relationship between the intermolecular interactions and electrode performance (i.e., K+‐solvent co‐insertion, or reversible K+ (de)intercalation) at the molecular scale, facilitating the design of high safety and high energy density potassium‐ion sulfur batteries. This study sheds light on the importance of intermolecular interactions to tune electrolyte properties and also opens new avenues for designing electrolytes for safe and practical PIBs. [ABSTRACT FROM AUTHOR]

BACKGROUND RESULTS CONCLUSION Regulation of the immune system to maintain homeostasis in the organism has become a focus of research, and the synergistic effect of multi‐component complexes will effectively improve the immunomodulatory activity. The present study aimed to investigate the interaction and synergistic immunomodulatory activity of isochlorogenic acid A (IAA) and Lycium barbarum glycopeptide (LbGp).The results obtained indicated that non‐covalent intermolecular interactions were employed to form the LbGp–IAA complex, with a binding ratio of 135.15 mg g−1. The formation of LbGp–IAA complex altered the conformation of LbGp, and IAA was mainly bound to LbGp by van der Waals forces and hydrogen bonds. In addition, LbGp–IAA promoted the proliferation of RAW264.7 cells. The IAA and LbGp interaction had a synergistic effect on the promotion of phagocytosis and the expression of nitric oxide, tumor necrosis faction‐α and interleukin‐1β, which improved the immunomodulatory effect of LbGp. Furthermore, the combination of LbGp and IAA synergistically inhibited lipopolysaccharide‐induced inflammatory response.In summary, the binding of IAA enhanced the immunomodulatory activity of LbGp and coordinated the immune response, and did not trigger an inflammatory response, which was potentially attributed to the alteration of spatial structure of LbGp through the binding of IAA. The results provide new perspectives for the study of glycopeptide–polyphenol interactions. © 2024 Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

Constructing organic materials with rigid‐planar molecules provides a unique platform for obtaining efficient photoluminescence (PL) by suppressing vibrational relaxation and extending the π‐conjugation. However, the presence of H‐aggregates/excimers resulting from interactions between π electrons and lone pairs during crystalization leads to aggregation‐caused quenching. Here, an alternative pressure‐treatment approach is presented for regulating molecular assembly to brighten rigid‐planar phthalic anhydride (PA) crystals with initial non‐emission. The pressure‐treated PA crystals exhibit significant blue‐light emission under ambient conditions, accompanied by a PL quantum yield of up to 15.7% and Commission International de I'Eclairage color coordinates of (0.20, 0.19). Detailed experiments and calculations reveal that pressure‐treated hydrogen bonds promote the planar rotation among PA molecules, which facilitates intermolecular π‐conjugation. This extended π‐conjugation alters the exciton relaxation channel, thereby triggering blue‐light emission based on charge transfer (CT) states. Remarkably, the obtained PA crystals also exhibit linear piezochromism (4.56 nm GPa−1) as a result of the structural sensitivity of the CT process. This work demonstrates the feasibility of regulating molecular assembly to achieve solid‐state emission in rigid‐planar molecules with initial non‐emission and opens up a new platform toward stimuli‐responsive crystalline materials. [ABSTRACT FROM AUTHOR]

In the context of human active response to exponentially increasing data volumes, memristors have emerged as a focal point in systematic problem‐solving approaches. Particularly, organic memristors, characterized by excellent scalability, flexibility, and 3D stacking capabilities, have shown its tremendous potential in innovative electronic applications. However, the modulation of molecular assembly and interface interaction at the electrode surface poses a challenging task, despite their crucial role in determining the memristive performance. Herein, a collaborative method involving hydrophobic molecular design and interface engineering is proposed to generate high‐quality nanofilms with optimal photoelectric and electrochemical properties. By subjecting the bottom electrode to O2 plasma treatment and chemical modification using a hydrophobic ionic liquid poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide (PTFSI), the hydrophobic compound DN demonstrates exceptional affinity and stronger intermolecular interactions with the electrode surface. Consequently, the two‐terminal device array comprising Al/DN@PTFSI/ITO exhibits robust non‐volatile write‐once‐read‐many times (WORM) memory behavior, resulting in a tripling production yield from 30% to 92% along with a lower threshold voltage of 1.5 V, higher ON/OFF current ratio of 103 and excellent stability. This study presents a versatile approach to optimize the film assembly and material/electrode interface, thereby accelerating the development of organic memristors toward future applications. [ABSTRACT FROM AUTHOR]

Structurally flexible organic porous molecular arrays are promising for the development of vapochromic materials with superior detection performance. Exploring the photophysical control of vapochromic materials using these molecular arrays is important for the design of new vapochromic materials. However, difficulties arise in the formation and control of organic porous molecular arrays owing to weak and less‐oriented noncovalent forces and their tendency to arrange into energetically preferred high‐density configurations. Herein, an efficient strategy is presented to control molecular arrays by manipulating the shapes of donor–acceptor–donor system‐based molecular building blocks using positional isomerism and report on the correlation between controlled molecular arrays and vapochromic behavior. Depending on their shape (Z‐shaped, quasi‐Z‐shaped, or linear shape), the building blocks formed different molecular arrays that controlled the intermolecular interactions and void volumes. This led to differences in the final microstructural morphologies. Consequently, they exhibited different vapochromic behaviors, and an in‐depth understanding of the correlation between the molecular arrays and vapochromism/vapofluorochromism is obtained. [ABSTRACT FROM AUTHOR]

Although the layer‐by‐layer (LBL) processing can usually achieve an optimal bulk‐heterojunction morphology for high‐performance Organic photovoltaics (OPVs), the unambiguous working principles governing the morphology evolution are still lacking. To address this issue, here the phase‐separation kinetics of LBL processing are comprehensively studied using in situ spectroscopies, which are very sensitive to the intermolecular interactions, e.g. the molecular packing and D:A phase‐separation. Upon casting the nonfullerene acceptor (i.e., the BTP‐eC9) solution on top of the polymer donor, i.e., PM6, it is found that 1) the solvent will first swell the polymer and induce a polymer gel, 2) following the polymer gelation, the NFAs will immediately permeate into the cavities of polymer gel and form a molecular‐level D:A mixing, and 3) with the evaporation of the solvent, phase‐separation between the donor and acceptor occurs and results in a bulk‐heterojunction morphology as those achieved with blend‐cast processing. With these understandings, more diverse processing conditions have been purposely utilized to dictate the phase evolution process precisely. As a result, a high efficiency of 19.7% is reached, representing one of the best among binary OPVs. Therefore, this work deciphers phase‐separation kinetics of LBL processing and should pave the way toward advanced morphology control for high‐performance OPVs. [ABSTRACT FROM AUTHOR]

Due to the feature of the strong intermolecular interactions causing aggregation‐caused excitons quenching (ACQ) of solution process, realizing high‐performance solution‐processed organic light‐emitting diodes (OLEDs) based on thermally activated delayed fluorescence (TADF) emitters remains a formidable challenge nowadays. To address this issue, herein, a novel strategy is proposed to construct solution‐processable ternary exciplex emitters by utilizing the dendritic oligomer as the substrate, simultaneously realizing excellent solution‐process adaptability, good dispersibility to restrain harmful ACQ, and improved exciton utilization with multiple reverse intersystem crossing channels. Accordingly, dendritic oligomer‐based exciplex systems are constructed by combining small‐molecule donor and acceptor components with the multi‐carbazole‐substituted tetraphenylsilane‐core analog as substrate. And their film morphologies, photoluminescence quantum yields (ΦPLs), and non‐radiative decay rates of triplet excitons (knrTs) are significantly improved. Among them, DMAC‐DPS:PO‐T2T:SimCP3 exhibits the highest ΦPL of 97.5% and the lowest knrT of 1.0 × 103 s−1, and realizes the best maximum external quantum efficiency of 29.7% in solution‐processed OLED, which is comparable with the highest electroluminescence efficiencies of all solution‐processable emitters. Therefore, this work will provide a prospective pathway to develop efficient solution‐processable exciplex emitters and promote the progress of solution‐processed OLEDs. [ABSTRACT FROM AUTHOR]

Biomaterials such as spider silk and mussel byssi are fabricated by the dynamic manipulation of intra‐ and intermolecular biopolymer interactions. Organisms modulate solution parameters, such as pH and ion co‐solute concentration, to effect these processes. These biofabrication schemes provide a conceptual framework to develop new dynamic and responsive abiotic soft material systems. Towards these ends, the chemical diversity of readily available ionic compounds offers a broad palette to manipulate the physicochemical properties of polyelectrolytes via ion‐specific interactions. In this study, we show for the first time that the ion‐specific interactions of biomimetic polyelectrolytes engenders a variety of phase separation behaviors, creating dynamic thermal‐ and ion‐responsive soft matter that exhibits a spectrum of physical properties, spanning viscous fluids to viscoelastic and viscoplastic solids. These ion‐dependent characteristics are further rendered general by the merger of lysine and phenylalanine into a single, amphiphilic vinyl monomer. The unprecedented breadth, precision, and dynamicity in the reported ion‐dependent phase behaviors thus introduce a broad array of opportunities for the future development of responsive soft matter; properties that are poised to drive developments in critical areas such as chemical sensing, soft robotics, and additive manufacturing. [ABSTRACT FROM AUTHOR]

In the pursuit of next‐generation ultrahigh‐energy‐density Li−O2 batteries, it is imperative to develop an electrolyte with stability against the strong oxidation environments. N,N‐dimethylacetamide (DMA) is a recognized solvent known for its robust resistance to the highly reactive reduced oxygen species, yet its application in Li−O2 batteries has been constrained due to its poor compatibility with the Li metal anode. In this study, a rationally selected hydrofluoroether diluent, methyl nonafluorobutyl ether (M3), has been introduced into the DMA‐based electrolyte to construct a localized high concentration electrolyte. The stable −CH3 and C−F bonds within the M3 structure could not only augment the fundamental properties of the electrolyte but also fortify its resilience against attacks from O2− and 1O2. Additionally, the strong electron‐withdrawing groups (−F) presented in the M3 diluent could facilitate coordination with the electron‐donating groups (−CH3) in the DMA solvent. This intermolecular interaction promotes more alignments of Li+‐anions with a small amount of M3 addition, leading to the construction of an anion‐derived inorganic‐rich SEI that enhances the stability of the Li anode. As a result, the Li−O2 batteries with the DMA/M3 electrolyte exhibit superior cycling performance at both 30 °C (359th) and −10 °C (120th). [ABSTRACT FROM AUTHOR]

Starch is considered an ideal alternative to petroleum‐based plastics. However, the application of thermoplastic starch (TPS), which produced from cassava starch plasticized with glycerol, is limited by its hydrophilic, poor mechanical properties, and inadequate processability. In this study, dialdehyde starch (DAS) is used as crosslinker to modify TPS/poly(vinyl alcohol) (PVA), and DAS crosslinked cassava starch/PVA blends are fabricated by melt mixing method. Studies on the molecular structure of DAS crosslinked cassava starch/PVA blend indicate that the addition of DAS enhances the intermolecular interactions between cassava starch and PVA, resulting in the formation of a dense internal structure. The plasticizing torque and equilibrium torque of crosslinked cassava starch/PVA blends are increased and the tensile strength reaches 3.60 MPa, an improvement of 186% compared with TPS. Additionally, the water contact angle increases from 87.8° to 119.6° after modification. Compared with other crosslinkers, DAS has obvious advantages, making the DAS crosslinked cassava starch/PVA blend a biodegradable material with excellent properties and promising application prospects. [ABSTRACT FROM AUTHOR]

Blue tetradentate Pt(II) complexes, Pt‐tBuCz and Pt‐dipCz, are synthesized by introducing carbazoles with bulky substituents for improving the rigidity and inhibiting intermolecular interactions of phosphorescent emitter. tert‐Butyl and 2,6‐diisopropylphenyl groups are substituted as the blocking groups at 3 position of the carbazole in Pt‐tBuCz and Pt‐dipCz, respectively. These new phosphorescent emitters exhibit a narrow full width at half maximum (FWHM) and a high horizontal emitting dipole orientation ratio. Pt‐dipCz demonstrates a small FWHM of 24 nm, a high emitting dipole orientation ratio of 81%, and a high photoluminescence quantum yield value of 94%. As a result, the Pt‐tBuCz and Pt‐dipCz devices exhibited external quantum efficiencies (EQEs) of 23.7% and 25.0% with small FWHMs of 25 and 22 nm, respectively. For the Pt‐dipCz device, the small FWHM and high EQE of >20% are maintained even at a doping concentration of 20 wt%. Furthermore, phosphor‐sensitized organic light‐emitting diodes fabricated using Pt‐dipCz as a sensitizer achieved a high EQE of 31.4% with an FWHM of 18 nm. This result indicates that the 2,6‐diisopropylphenyl group is a effective blocking group for Pt(II) complexes to develop highly efficient, color stable, doping concentration resistant, and efficiently sensitizing blue phosphors. [ABSTRACT FROM AUTHOR]

Herein, we have designed aqueous dispersed self‐assembled nanostructures with diverse morphologies from the zinc tetraphenyl porphyrin (ZnTPP) monomer employing simple solution‐based coprecipitation methods. Detailed morphological studies have been carried out by various electron microscopy techniques. Finally, the structural features were correlated with the underpinning photophysical processes using steady‐state and time‐resolved spectroscopy. Detailed studies suggest that controlled morphology and highly defined intermolecular interactions affect the overall photoinduced charge transfer process. Based on the fundamental investigations, all these different types of nanostructures have been utilized as photocatalysts for solar hydrogen production without using any cocatalysts, and it was found that the spherical nanostructure exhibits significantly higher H2 production rates of ∼1682 μ mole/g, which is a few folds higher than other 1D and 2D nanostructured materials. The experimental findings were further supported by the TD‐DFT study. Furthermore, the detailed computational studies suggest that the spherical aggregates exhibited a more vital interaction between the ZnTPP molecules, causing significant electronic coupling between bright local excited and charge transfer states, which supports our experimental findings. Finally, we have selectively utilized the oxidative half‐reaction for the simultaneous transformation of glycerol to valuable chemicals along with photocatalytic H2 production through reductive half‐reaction. [ABSTRACT FROM AUTHOR]

We report the crystal structures of three matrine derivatives, namely, the salts (1R,2R,9S,17S)‐6‐oxo‐7,13‐diazatetracyclo[7.7.1.02,7.013,17]heptadecan‐13‐ium (2E)‐3‐(3,4‐dihydroxyphenyl)prop‐2‐enoate (matrine caffeinate) sesquihydrate, C15H25N2O+·C9H7O4−·1.5H2O (Matrine–CA), and the 2‐hydroxybenzoate (salicylate) monohydrate, C15H25N2O+·C7H5O3−·H2O (Matrine–SA), as well as the 1.75‐hydrate form, (1R,2R,9S,17S)‐7,13‐diazatetracyclo[7.7.1.02,7.013,17]heptadecan‐6‐one 1.75‐hydrate, C15H24N2O·1.75H2O (Matrine–H). Each derivative exhibited a consistent molecular conformation for the matrine core, which is notably distinct from that of the anhydrous form. Notably, both salts crystallized in the orthorhombic space group P212121, with an asymmetric unit featuring one cation and one anion. Within the two salt structures, intermolecular proton transfer between matrine and the acid is observed, culminating in the formation of a matrine cation protonated at the tertiary amine N site. The Matrine–CA crystal packing is manifested as a three‐dimensional (3D) network arising from one‐dimensional (1D) supramolecular helical chains, stabilized by N—H...O and O—H...O hydrogen bonds. In the case of Matrine–SA, the matrine cation is interconnected via hydrogen bonds with salicylate anions and water molecules, also forming a 1D helical motif. The structure of the hydrate form, Matrine–H, is reported again with the disordered solvent molecules accurately located. To further elucidate the structural attributes, Hirshfeld surface analysis and fingerprint plots are employed, offering a nuanced perspective on the intermolecular contacts and interactions within these crystalline forms. [ABSTRACT FROM AUTHOR]

A μ‐peroxido‐bis[di‐triethylamine N‐oxide‐dichloro‐dioxouranium] complex with the formula [(UO2)2O2(ON(CH2CH3)3)4Cl2] (complex 1) was synthesized photochemically from a reaction containing uranyl chloride, triethylamine, and H2O2. The photochemical breakdown of H2O2 yielded ⋅OH radicals that reacted with triethylamine to form triethylamine N‐oxide (TEAO) in situ, which subsequently coordinated to UO22+ cations in a monodentate fashion via the N‐oxide functional groups. Structure determination using single crystal X‐ray diffraction revealed that TEAO ligands also formed intermolecular and intramolecular hydrogen bonds with UO22+ and peroxide moieties, and the intermolecular H‐bonding interactions displayed a temperature dependence with Oyl ‐ ‐ H−C and Oper ‐ ‐ H−C distances shortening at 100(2) K by ca. 0.1 Å. Raman spectroscopy data were collected on single crystals of 1 and peak fitting of these results allowed for assignments of peaks including C−N stretches for TEAO ligands bound to UO22+ cations at 696.8 cm−1, 717.8 cm−1, and 776.5 cm−1, which are redshifted by 30–40 cm−1 when compared to free triethylamine. UO22+ν1 and O22−ν1 stretches, U−Oper stretches, and notably, U−Cl stretches were all identified as well, with U−Cl modes at 198.9 cm−1 and 212.1 cm−1 substantially redshifted compared to the uranyl chloride starting material. [ABSTRACT FROM AUTHOR]

Achieving high electrical conductivity (σ) and power factor (PF) simultaneously remains a significant challenge for n‐type organic themoelectrics (OTEs). Herein, we demonstrate the state‐of‐the‐art OTEs performance through blending a fused bithiophene imide dimer‐based polymer f‐BTI2g‐SVSCN and its selenophene‐substituted analogue f‐BSeI2g‐SVSCN with a julolidine‐functionalized benzimidazoline n‐dopant JLBI, vis‐à‐vis when blended with commercially available n‐dopants TAM and N‐DMBI. The advantages of introducing a more lipophilic julolidine group into the dopant structure of JLBI are evidenced by the enhanced OTEs performance that JLBI‐doped films show when compared to those doped with N‐DMBI or TAM. In fact, thanks to the enhanced intermolecular interactions and the lower‐lying LUMO level enabled by the increase of selenophene content in polymer backbone, JLBI‐doped films of f‐BSeI2g‐SVSCN exhibit a unprecedent σ of 206 S cm−1 and a PF of 114 μW m−1 K−2. Interestingly, σ can be further enhanced up to 326 S cm−1 by using TAM dopant as a consequence of its favorable diffusion behavior into densely packed crystalline domains. These values are the highest to date for solution‐processed molecularly n‐doped polymers, demonstrating the effectiveness of the polymer‐dopant matching approach carried out in this work. [ABSTRACT FROM AUTHOR]

This research commenced with an exploration of how metal nodes in metal‐organic frameworks (MOFs) influence photodynamic therapy (PDT) outcomes. Ultimately, it is revealed that intermolecular interactions are the core mechanism determining the optical properties and PDT efficacy of MOFs. An advanced system of MOFs based on the integration of twelve rare earth ions (RE3+) with boron dipyrromethene (BODIPY)‐derived ligands is reported. Intriguingly, this series of MOFs exhibits a reverse relationship between the radius of RE3+ and PDT efficacy. Single‐crystal X‐ray diffraction analyses along with theoretical calculations indicate that varying RE3+ results in a spatial displacement of the ligands along the dipole direction, diminishing electrostatic (dipole–dipole) interactions while enhancing dispersion (π–π) interactions, thereby enhancing the generation of triplet excitons. Consequently, a novel parameter, Ae‐v = EvdW / Eint × 100%, is proposed to quantify the interplay between non‐radiative energy dissipation via electrostatic interactions and efficient energy utilization in generating singlet oxygen through dispersion interactions. Furthermore, with consistent acoustic sensitivity aligned with the sonoluminescence mechanism, RE‐DCBs are employed in sono‐photodynamic cancer therapy, attaining significant therapeutic results in tumor treatment during in vivo experiments. [ABSTRACT FROM AUTHOR]

One of the most recent focuses in supramolecular chemistry is developing molecules designed to exhibit programmable properties at the molecular level. Rotaxanes, which function as molecular machines with movements controlled by external stimuli, are prime candidates for this purpose. However, the controlled synthesis of rotaxanes, especially amide‐benzylic rotaxanes with more than two components, remains an area ripe for exploration. In this study, we aim to elucidate the formation of amide‐benzylic [3]rotaxanes using a thread that includes a conventional succinamide station and an innovative triazole‐carbonyl station. Including the triazole‐carbonyl station introduces new perspectives into the chemistry of rotaxanes, influencing their conformation and dynamics. The synthesis of two‐station rotaxanes with varying stoppers demonstrated that the macrocycle consistently occupies the succinamide station, providing greater stability as evidenced by NMR and SC‐XRD analyses. The presence of a triazole‐carbonyl station facilitated the formation of a second macrocycle exclusively when a secondary amide was employed as the stopper group, presumably due to decreased steric hindrance. Moreover, the second macrocycle directly forms at the triazole‐carbonyl station. This investigation reveals that slight modifications in the thread structure can dramatically impact the formation, stability, and interactions between components of rotaxanes. [ABSTRACT FROM AUTHOR]

The reaction of 2‐amino‐4,6‐dimethylpyridine with 4‐cyanobenzaldehyde, salicylaldehyde or 2‐hydroxy‐1‐naphthaldehyde furnished the corresponding N‐aryl‐(2‐pyridyl)aldimines in very good yields. The synthetised Schiff bases were characterized by FT‐IR, 1H, 13C, DEPT‐135 and [1H,13C]‐HSQC NMR spectroscopy, HRMS and elemental analyses. Additionally, the structure of 2‐((E)‐(4,6‐dimethylpyridin‐2‐ylimino)methyl)phenol was unambiguously determined by single crystal X‐ray diffraction analysis. Hirshfeld analysis of molecular packing was performed. The most common intermolecular interaction is the hydrogen‐hydrogen (56.8 %) contacts while the most significant interactions are the O...H (6.5 %) and C...C (4.2 %) contacts. DFT calculated geometric parameters and NMR chemical shifts are well correlated with the experimental data. This compound has a net dipole moment of 2.4261 Debye. The MCF‐7 growth was suppressed by N‐aryl‐(2‐pyridyl)aldimines more than that for T47D cell line. The IC50 values of 4‐((E)‐(4,6‐dimethylpyridin‐2‐ylimino)methyl)benzonitrile against MCF‐7 and T47D cell lines were the lowest and it is considered the most promising candidate as anticancer agent. Furthermore, this study conducted a molecular docking of benzonitrile‐based Schiff base onto DNA duplex to explore a potential molecular mechanism for the robust anticancer activities of this Schiff base adduct. The molecular docking results indicate that benzonitrile‐based Schiff base exhibits characteristics of a potential DNA minor groove binder. [ABSTRACT FROM AUTHOR]

Developing non‐halogenated solvent‐processed organic solar cells (OSCs) demands precise control over the bulk‐heterojunction (BHJ) morphology of the photoactive layer. However, the limited solubility of halogen‐free solvents to photoactive materials hinders microstructure morphology fine‐tuning for boosting photovoltaic performance. This study not only examines the debated intermolecular interactions between the DBrDIB solid additive and photoactive materials but also analyzes the substantial influence of volatile solid additive on the BHJ morphological properties. The DBrDIB effectively restricts the excessive aggregation of Y6‐BO and regulates the phase separation, which is attributed to strong intermolecular interactions with Y6‐BO and rapid quenching during morphology formation. It then achieves a well‐mixed D/A phase with favorable domain size, resulting in a balanced aggregation and dispersion of D/A, ultimately leading to markedly enhanced charge transfer and transport as well as suppressed charge recombination. The transformative use of the o‐xylene/DBrDIB solvent system propels PM6:Y6‐BO and PM6:Y6‐HU OSCs to impressive efficiencies of 17.9% and 19.1%, respectively, outperforming those of the control devices. These findings provide crucial insights into theoretical and experimental areas, offering actionable guidelines for designing high‐performance OSCs processed from halogen‐free solvent. [ABSTRACT FROM AUTHOR]

Ion‐conductive elastomers have emerged as ideal candidates for ionic skin and wearable devices due to their intrinsic stretchability and excellent electrical properties. Despite continuous efforts in this field, strain‐stiffening, robust yet compliant ionic elastomers are still unattainable due to the limited intermolecular interactions, restricting their reliability and durability in practical applications. Inspired by the interwoven collagen fiber network and synergistic non‐covalent interaction in the dermis, an immense strain‐stiffening, ultra‐stretchable, highly tough, and elastic ionic elastomer are reported by introducing the metal–oxygen interactions into the highly entangled network. The ionic elastomers also show intriguing self‐healing ability, high adhesion, and environmental tolerance, contributed by the dynamic synergistic noncovalent interactions. The prepared ionic skin displays sensitive and stable responses to temperature and strain. This work demonstrates a new design strategy for fabricating high‐performance ionic elastomers with excellent mechanical and electrical properties, showing great prospects in wearable and flexible devices. [ABSTRACT FROM AUTHOR]

Triboluminescence is a phenomenon in which light is generated through mechanical stress; it has emerging applications in stress‐sensing devices. Although the prevailing mechanistic model indicates that light emits from charge separation and recombination in fracture planes arising from polar structures, its application in designing triboluminescent materials remains limited owing to numerous exceptions. This study provides insights into the essential requirements for triboluminescence by investigating the structural and electrostatic properties of fractured crystals of copper thiocyanate complexes. The examined fracture plane indicated that charge pairs (which are essential for light emission) form when intermolecular interactions are disrupted during fracturing. On the basis of the nature of these charges, we successfully suppressed triboluminescence by inhibiting the formation of intermolecular interactions disrupted in the examined complexes. Furthermore, we induced its re‐emergence by creating an alternative fracture plane through controlled manipulation of the molecular network. This demonstrative deactivation and reactivation of triboluminescence underscores the critical role of intermolecular disruption in generating charge pairs, a prerequisite for triboluminescence. [ABSTRACT FROM AUTHOR]

BACKGROUND RESULTS CONCLUSION Stimuli‐responsive emulsions have garnered significant attention for their ability to enhance sensory qualities and control the release of encapsulated nutrient in emulsion‐based products. However, the characteristics of synthetic materials of fabricating stimuli‐responsive emulsions have been a crucial limitation in the food industry. Regulating the behavior of molecules at the interface could potentially achieve the desired stimuli‐responsive behavior, but currently there is limited information available.High‐internal‐phase emulsions (HIPEs) were fabricated for the encapsulation of allicin, stabilized by a complex of 20 g kg−1 whey protein amyloid fibrils (WPF) and 20 g kg−1 glycyrrhizin fibers (GA). The intermolecular interactions between WPF and GA in the fiber complexes were predominantly governed by hydrophobic and electrostatic forces. These complexes adsorbed and stacked around the oil droplets, forming a protective interfacial film that enhanced droplet stability. An increased proportion of WPF (WPF = 3:1 or 4:1) surrounding the oil droplets enhanced the accelerated storage stability of HIPEs, with instability indexes approaching 0.2. Additionally, HIPEs displayed a temperature‐dependent modulus, with the emulsion stabilized by a WPF ratio of 3:1 showing the highest modulus at 85 °C. The encapsulation efficiency of allicin in HIPEs ranged from 88.69 ± 6.62% to 101 ± 1.37% at 25 °C, and from 31.95 ± 1.92% to 78.69 ± 4.63% after incubation at 85 °C for 8 h. The release profile of allicin from the HIPEs exhibited thermal responsiveness, depending on the interfacial content of GA.These findings indicated that the thermal‐responsive properties of HIPEs can be strategically engineered by manipulating their interfacial characteristics. © 2024 Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

Comprehensive Summary Considering their oriented crystalline structure and high luminescent efficiency, the exploration of multi‐component organic cocrystal systems with tunable supramolecular nanostructures and potential RGB light emission has emerged as a captivating but challenging subject. Here, we propose a straightforward synthetic strategy to precisely govern the assembly, structure and structure‐property relationship of organic cocrystals. By employing the single‐crystalline template‐assisted epitaxial growth (SCT‐EG) method, the two‐dimensional (2D) highly‐aligned cocrystal nanomeshes are firstly developed to afford an exceptional RGB trichromatic system, triggering cross‐modulation white light emission (WLE) with remarkable stability and regeneration capacity over six months. The transformation from random 1D microstructures to uniformly‐oriented 2D nanomeshes can be attributed to the regulatory competitive intermolecular π‐π, CT interactions, and partial H bond interactions among cocrystals. Moreover, the successful construction of 2D RGB trichromatic cocrystal nanomeshes system holds promise to generate full‐color display, which can function as multicolor inks for photonic dynamic recognition, information encryption, and decryption. [ABSTRACT FROM AUTHOR]

Herein, we propose a regional functionalization molecular design strategy that enables independent control of distinct pivotal parameters through different molecule segments. Three novel multiple resonances thermally activated delayed fluorescence (MR‐TADF) emitters A‐BN, DA‐BN, and A‐DBN, have been successfully synthesized by integrating highly rigid and three‐dimensional adamantane‐containing spirofluorene units into the MR framework. These molecules form two distinctive functional parts: part 1 comprises a boron‐nitrogen (BN)‐MR framework with adjacent benzene and fluorene units forming a central luminescent core characterized by an exceptionally rigid planar geometry, allowing for narrow FWHM values; part 2 includes peripheral mesitylene, benzene, and adamantyl groups, creating a unique three‐dimensional "umbrella‐like" conformation to mitigate intermolecular interactions and suppress exciton annihilation. The resulting A‐BN, DA‐BN, and A‐DBN exhibit remarkably narrow FWHM values ranging from 18 to 14 nm and near‐unity photoluminescence quantum yields. Particularly, OLEDs based on DA‐BN and A‐DBN demonstrate outstanding efficiencies of 35.0 % and 34.3 %, with FWHM values as low as 22 nm and 25 nm, respectively, effectively accomplishing the integration of high color purity and high device performance. [ABSTRACT FROM AUTHOR]

Modulating the arrangement of superstructures through noncovalent interactions has a significant impact on macroscopic shape and the expression of unique properties. Constructing π‐interaction‐driven hierarchical three‐dimensional (3D) superstructures poses challenges on account of limited directional control and weak intermolecular interactions. Here we report the construction of a 3D diamondoid superstructure, named π‐Diamond, employing a ditopic strained Z‐shaped building block comprising a porphyrin unit as bow‐limb double‐strapped with two m‐xylylene units as bowstrings. This superstructure, reminiscent of diamond's tetrahedral carbon composition, is composed of double‐walled tetrahedron (DWT) driven solely by π‐interactions. Hetero‐π‐stacking interactions between porphyrin and m‐xylylene panels drive the assembly of four building blocks predominantly into a DWT, which undergoes extension to create an adamantane unit and eventually a diamondoid superstructure wherein each porphyrin panel is shared by two neighboring tetrahedra through hetero‐π‐stacking. π‐Diamond exhibits a solid‐state fluorescent quantum yield 44 times higher than that of tetraphenylporphyrin along with excellent photocatalytic performance. The precise 3D directionality of π‐interactions, achieved through strained multipanel building blocks, revolutionizes the assembly of hierarchical 3D superstructures driven by π‐interactions. [ABSTRACT FROM AUTHOR]

Among the various types of materials with intrinsic porosity, porous organic cages (POCs) are distinctive as discrete molecules that possess intrinsic cavities and extrinsic channels capable of facilitating molecular sieving. However, the fabrication of POC membranes remains highly challenging due to the weak noncovalent intermolecular interactions and most reported POCs are powders. In this study, we constructed crystalline free‐standing porous organic cage membranes by fortifying intermolecular interactions through the induction of intramolecular hydrogen bonds, which was confirmed by single‐crystal X‐ray analysis. To elucidate the driving forces behind, a series of terephthaldehyde building blocks containing different substitutions were reacted with flexible triamine under different conditions via interfacial polymerization (IP). Furthermore, density functional theory (DFT) calculations suggest that intramolecular hydrogen bonding can significantly boost the intermolecular interactions. The resulting membranes exhibited fast solvent permeance and high rejection of dyes not only in water, but also in organic solvents. In addition, the membrane demonstrated excellent performance in precise molecular sieving in organic solvents. This work opens an avenue to designing and fabricating free‐standing membranes composed of porous organic materials for efficient molecular sieving. [ABSTRACT FROM AUTHOR]

We show an unexpected aggregation phenomenon of a long oligoyne (Py[16]) with 16 contiguous triple bonds and endcapped with bulky 3,5‐bi(3,5‐bis‐tert‐butylphenyl)pyridine groups. Aggregation of 1D π‐conjugated oligoyne chains is rare given the minimal π–π intermolecular interactions as well as its flexibility that works against self‐assembly. In dilute solutions, the reversible aggregation of Py[16] initiates at low temperature in the range of 140–180 K, and is not observed for shorter oligoynes in this series. Cryogenic UV/Vis electronic absorption spectra and vibrational Raman spectra with different laser wavelength lines tuning from in‐resonance to off‐resonance conditions have been used to extract the vibrational features characterizing the monomer and aggregate species. Theoretical calculations complement the spectroscopic findings. [ABSTRACT FROM AUTHOR]

Two novel diamines 1‐(4‐aminophenyl)‐1,3,3‐trimethyl‐2,3‐dihydro‐1H‐indene‐5‐amine and 4‐amino‐N‐(4‐(5‐(4‐aminobenzamide)‐1,3,3‐trimethyl‐2,3‐dihydro‐1H‐inden‐1‐yl) phenyl) benzamide containing indene and amide groups were successfully designed and synthesized, and a series of colorless polyimides (CPIs) derived from the two diamines with 1,2,4,5‐cyclohexanetetracarboxylic dianhydride in various ratios were copolymerized. The introduction of aliphatic ring structures was conducive to the improvement of optical properties, while the incorporation of amide groups improved thermal and mechanical properties. These CPI films exhibited excellent optical properties (T400 > 80%), high heat resistance (Tg > 300 °C) and mechanical properties with the synergistic action of the two groups. Furthermore, the effect of the content of amide groups on the intermolecular interaction of CPIs was systematically analyzed. This study provides a fancy method for the development of heat‐resistant colorless materials for optical applications. [ABSTRACT FROM AUTHOR]

The coacervation of alpha‐synuclein (αSyn) into cytotoxic oligomers and amyloid fibrils are considered pathological hallmarks of Parkinson's disease. While aggregation is central to amyloid diseases, liquid–liquid phase separation (LLPS) and its interplay with aggregation have gained increasing interest. Previous work shows that factors promoting or inhibiting aggregation have similar effects on LLPS. This study provides a detailed scanning of a wide range of parameters, including protein, salt and crowding concentrations at multiple pH values, revealing different salt dependencies of aggregation and LLPS. The influence of salt on aggregation under crowding conditions follows a non‐monotonic pattern, showing increased effects at medium salt concentrations. This behavior can be elucidated through a combination of electrostatic screening and salting‐out effects on the intramolecular interactions between the N‐terminal and C‐terminal regions of αSyn. By contrast, this study finds a monotonic salt dependence of LLPS due to intermolecular interactions. Furthermore, it observes time evolution of the two distinct assembly states, with macroscopic fibrillar‐like bundles initially forming at medium salt concentration but subsequently converting into droplets after prolonged incubation. The droplet state is therefore capable of inhibiting aggregation or even dissolving aggregates through heterotypic interactions, thus preventing αSyn from its dynamically arrested state. [ABSTRACT FROM AUTHOR]

In this study, three stable tetradentate Pt(II) complexes are synthesized and characterized, namely, Pt‐biPh, Pt‐biPh5tBu, and Pt‐biPh4tBu, tailored for blue phosphorescent organic light‐emitting diodes to realize high‐efficiency and narrowband emissions via ligand engineering. Biphenyl (Pt‐biPh) or tert‐butyl‐modified biphenyl (Pt‐biPh5tBu and Pt‐biPh4tBu) is introduced into the carbene unit of the ligand to control the intermolecular interactions between the Pt(II) phosphors. Pt‐biPh, Pt‐biPh5tBu, and Pt‐biPh4tBu exhibit high photoluminescence quantum yields of 74%, 84%, and 92% with exciton lifetimes of 2.2, 2.3, and 2.5 µs, respectively, demonstrating rapid and efficient light emission. Furthermore, Pt‐biPh, Pt‐biPh5tBu, and Pt‐biPh4tBu show maximum external quantum efficiency (EQE) values of 18.1%, 19.0%, and 21.8%, respectively. Pt‐biPh5tBu and Pt‐biPh4tBu exhibit narrowband emission with a full width at half maximum of 21 nm owing to the small vibrational emission because of their sterically hindered and bulky ligand structures. Moreover, phosphor‐sensitized thermally activated delayed fluorescence devices employing a Pt‐biPh4tBu sensitizer achieve a high EQE of 28.6%. In particular, Pt‐biPh4tBu performs better than the state‐of‐the‐art phosphor as the sensitizer of the blue phosphor‐sensitized thermally activated delayed fluorescence devices in terms of the EQE. [ABSTRACT FROM AUTHOR]

Multiple resonance thermally activated delayed fluorescence (MR‐TADF) emitters are promising for high‐definition organic light‐emitting diodes (OLEDs) due to their high exciton utilization and color purity. However, strong interchromophore interactions cause most MR‐TADF emitters with planar structures to aggregate at high doping concentrations, leading to degraded efficiencies. Herein, using benzenesulfonyl‐functionalized dibenzothiophene sulfoximine with steric effects, three MR‐TADF emitters (2SBN, 3SBN, and 4SBN) are synthesized by coupling the classic DtBuCzB skeleton at different sites. Three emitters exhibit green or blue‐green emission with full width at half maximum (FWHM) values less than 29 nm and photoluminescence quantum yields exceeding 90%. OLEDs based on 2SBN, 3SBN, and 4SBN achieve high maximum external quantum efficiency (EQEmax) values of 30.1%, 27%, and 33.8%, respectively, at a 5 wt.% doping concentration. Notably, due to the distorted conformation of 4SBN and suppressed intermolecular interaction, the OLED remains high EQEmax of 28.9% at a doping concentration of 20 wt.%. These results demonstrate the feasibility of molecular design to modulate spatial conformations via positional isomerism to develop MR‐TADF emitters with reduced concentration quenching. [ABSTRACT FROM AUTHOR]

Comprehensive Summary pH is an important stimuli‐responsive signal because deprotonation‐protonation process is crucial for many life functions. Photoacid is a kind of photoresponsive group that can release protons upon irradiation. This property makes invasive pH control can be replaced by noninvasive light control. However, photoacid is rare. In this work, macrocyclic calixpyridinium was found to be used as a photoacid to release protons from acidic methylene under the irradiation of a 254 nm UV lamp. When the solution of calixpyridinium−disulfonated xantphos aggregates were irradiated by a 254 nm portable UV lamp, disulfonated xantphos was able to receive the protons released from calixpyridinium. This noninvasive photocontrolled proton transfer not only replaces an invasive pH regulation but also achieves a synergistic function. The deprotonation of calixpyridinium and the protonation of disulfonated xantphos can occur simultaneously to disrupt the aggregates. Moreover, the photoresponsive disassembly is reversible by heating. This photoresponsive material was further applied as a photocontrolled release model. In addition, a dissipative assembly was successfully designed based on this photoresponsive disassembly. This study supplies a generalized strategy to construct pH‐responsive biocompatible materials with light‐control properties by using macrocyclic calixpyridinium and its matched various guests in water. [ABSTRACT FROM AUTHOR]

Organic luminescent solid materials have attracted much attention due to practical applications such as sensor materials and optical waveguides. We have previously reported that inverse type diarylethenes exhibit strong emission in crystal without causing aggregation‐caused quenching. However, the emission color was limited to mainly green. To tune the emission color, in this work, we newly synthesized inverse type diarylethenes having a shortened π‐conjugation length or a polar substituent and investigated their fluorescence properties in solutions and crystals. The crystals exhibited various emission colors from blue, green, yellow to red depending on the molecular structure. The emission color changes of the crystals were induced by the intermolecular interactions such as CH‐π interactions in addition to the shortened π‐conjugation length and the intramolecular charge transfer character. [ABSTRACT FROM AUTHOR]

The crystal structures of two coordination compounds, (acetato‐κO)(2,2′‐bipyridine‐κ2N,N′)(1,10‐phenanthroline‐κ2N,N′)copper(II) acetate hexahydrate, [Cu(C2H3O2)(C10H8N2)(C12H8N2)](C2H3O2)·6H2O or [Cu(bipy)(phen)Ac]Ac·6H2O, and (acetato‐κO)bis(2,2′‐bipyridine‐κ2N,N′)copper(II) acetate–acetic acid–water (1/1/3), [Cu(C2H3O2)(C10H8N2)2](C2H3O2)·C2H4O2·3H2O or [Cu(bipy)2Ac]Ac·HAc·3H2O, are reported and compared with the previously published structure of [Cu(phen)2Ac]Ac·7H2O (phen is 1,10‐phenanthroline, bipy for 2,2′‐bipyridine, ac is acetate and Hac is acetic acid). The geometry around the metal centre is pentacoordinated, but highly distorted in all three cases. The coordination number and the geometric distortion are both discussed in detail, and all complexes belong to the space group P. The analysis of the geometric parameters and the Hirshfeld surface properties dnorm and curvedness provide information about the metal–ligand interactions in these complexes and allow comparison with similar systems. [ABSTRACT FROM AUTHOR]

It is well known that Hirshfeld surfaces provide an easy and straightforward way of analysing intermolecular interactions in the crystal environment. The use of atomic Hirshfeld surfaces has also demonstrated that such surfaces carry information related to chemical bonds which allow a deeper evaluation of the structures. Here we briefly summarize the approach of atomic Hirshfeld surfaces while further evaluating the kind of information that can be retrieved from them. We show that the analysis of the metal‐centre Hirshfeld surfaces from structures refined via Hirshfeld Atom Refinement (HAR) allow accurate evaluation of contacts of type M...H, and that such contacts can be related to the overall shape of the surfaces. The compounds analysed were tetraaquabis(3‐carboxypropionato)metal(II), [M(C4H3O4)2(H2O)4], for metal(II)/M = manganese/Mn, cobalt/Co, nickel/Ni and zinc/Zn. We also evaluate the sensitivity of the surfaces by an investigation of seemingly flat surfaces through analysis of the curvature functions in the direction of C—C bonds. The obtained values not only demonstrate variations in curvature but also show a correlation with the hybridization of the C atoms involved in the bond. [ABSTRACT FROM AUTHOR]

BACKGROUND: The present study aimed to determine how various amounts (0.00, 0.58, 1.52 and 4.50 g 100 g−1) of wine lees (WL), which contains numerous essential components, impact the emulsifying properties of fish gelatin (FG) at a low concentration (0.5 g 100 g−1) in the high‐fat phase (65 g 100 g−1). This study conducted rheology, physicochemical technical and characterization analyses on the emulsions to provide sustainable and innovative approaches for spreadable oils. RESULTS: The addition of WL to FG emulsions improved oxidative stability, emulsion stability and bioactive compounds. The zeta potential (−101 ± 5.62 mV) of 0.58 g 100 g−1 WL‐containing emulsion (PE1) was found to be high, whereas particle size (347.6 ± 5.25 nm) and polydispersity index (0.50) were statistically low. It was also found that the addition of WL improved the intermolecular interactions, crystallinity and microstructural properties of the emulsions. All these results were supported by simulating the molecular configuration between FG and WL. The compounds gallic acid, caffeic acid, myricetin, quercetin and resveratrol showed a strong affinity to FG, with free binding energies of −5.50, −5.88, −6.53, −6.68 and −6.66 kcal mol−1, respectively. CONCLUSION: As a result, WL‐supported FG has the potential to be used as an alternative to egg proteins to develop sustainable low‐cost spreadable emulsions. © 2024 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

High performance deep‐blue emitters with a Commission International de l'Eclairage (CIE) coordinate of CIEy≤0.08 are highly desired in ultrahigh‐definition displays. Herein, we designed and synthesized an efficient D–π–A deep‐blue emitter, 2‐(6‐([1,1′ : 3′,1′′‐terphenyl]‐5′‐yl)pyridin‐3‐yl)‐1‐phenyl‐1H‐phenanthro[9,10‐d] imidazole (mPTPH), using the synergistic effect of intramolecular hydrogen bond (H‐bond) and hybridized excited state. Single‐crystal structure analysis confirmed that there exist intra‐ and intermolecular H‐bond interactions which could inhibit the structure vibration and increase photoluminescence efficiency. The photophysical and theoretical results show that mPTPH exhibited hybridized local and charge‐transfer (HLCT) feature with strong deep‐blue emission. Ultimately, the non‐doped device based on mPTPH exhibited high maximum luminance of 20610 cd m−2. The doped device achieved high maximum external quantum efficiency of 5.4 % and small efficiency roll‐off with deep‐blue emission peak of 413 nm and CIE coordinate of (0.16, 0.08). [ABSTRACT FROM AUTHOR]

Recently, an ever‐growing interest has been paid on organic single‐molecule white light‐emitting materials for effective white organic light‐emitting diodes (WOLEDs). However, subject to Kasha's rule, photons can only be emitted from the lowest excited state and thus panchromatic or dual emissions are extremely forbidden, which results in a certain challenge in achieving white emission. Herein, a strategy of synergetic carbonyl and heptagonal structure is proposed for organic single‐molecule white light emission and demonstrated by TAO/TABO/TA2O organic luminescent materials that are modified on aryl ketones/amine fragments. Among them, due to the robust intermolecular interactions triggered by synergetic carbonyl and heptagonal structure, TA2O exhibits vibrant monomer and dimer photoluminescence with dual thermally activated delayed fluorescence (TADF) characteristics. As a result, the first single‐molecule dual‐TADF WOLED based on the synergetic system is successfully fabricated with an external quantum efficiency of 7.2%. This study not only expands the scope of carbonyl and heptagonal structure for novel optoelectronic properties and applications but also opens new avenues for the development of efficient single‐molecule WOLEDs with dual TADF mechanisms. [ABSTRACT FROM AUTHOR]

Flexible organic crystal materials with optical waveguide property have attracted much attention for various applications. Meanwhile, the rising demand for deep space and polar explorations have brought about a growing interest in materials with low temperature flexibility. However, the development of organic crystal materials integrating optical waveguide and low temperature elasticity remains a significant challenge. Here, three flexible organic crystals with bromo‐hydroxy chalcone backbone are developed via molecular engineering strategy. The 4BHIE crystal with 4‐bromo‐N‐ethyl substituent exhibits superior 2D elasticity under mechanical external forces with ≈180° bending and 1.30 mm of curvature. The low optical loss coefficient of only 0.309 dB mm−1 also demonstrates potential applications in flexible optoelectronic waveguides. Interestingly, the introduction of a longer alkyl chain onto N atom of indole moiety (4BHIB) exhibits more remarkable flexibility with 0.35 mm of curvature due to its richer and more complex network of intermolecular interactions compared with that of 4BHIE. Furthermore, 5BHIE crystal with 5‐bromo‐N‐ethyl substituent shows not only elasticity at room temperature but also low‐temperature elasticity in liquid nitrogen with reversible temperature response owing to the strengthening intermolecular interactions at low temperature. 5BHIE crystal displays potential optical waveguide application in low temperature environments. [ABSTRACT FROM AUTHOR]

The application of supramolecular assembly (SA) with room temperature phosphorescence (RTP) in aqueous phase has the potential to revolutionize numerous fields. However, using simple molecules with crystalline RTP to construct SA with aqueous phase RTP is hardly possible from the standpoint of forces. The reason lies in that the transition from crystal to SA involves a structure transformation from highly stable to more dynamic state, leading to increased non‐radiative deactivation pathways and silent RTP signal. Here, with the benefit of the confinement from the layered double hydroxide (LDH), various simple molecules (benzene derivatives) can successfully form metastable SA with aqueous phase RTP. The maximum of RTP lifetime and efficiency can reach 654.87 ms and 5.02 %, respectively. Mechanistic studies reveal the LDH energy trap can strengthen the intermolecular interaction, providing the prerequisite for the existence of metastable SA and appearance of aqueous phase RTP. The universality of this strategy will usher exploration into other multifunctional monomer, facilitating the development of SAs with aqueous phase RTP. [ABSTRACT FROM AUTHOR]

Vibration and noise severely affect the operation of mechanical equipment and is also detrimental to human health. Therefore, the development of high performance damping materials is crucial. However, current methods to improve damping properties often come at the expense of mechanical properties, resulting in inferior mechanical performance of materials. In order to address the issue of imbalance between damping properties and mechanical properties in polyurethane damping elastomers. In this study, polyester dangling chains containing polar groups are synthesized and introduced into polyurethane. The obtained polyurethane exhibited an effective damping temperature range of 154 °C (−54 °C to 100 °C) and a tensile strength of 15.82 MPa. Furthermore, dynamic mechanical analysis and broadband dielectric relaxation spectroscopy are combined to investigate the influence of polar dangling chains on the structure and properties of polyurethane. The degree of microphase separation increases after the introduction of polar dangling chains, indicating enhances intermolecular interaction forces, facilitating the formation of hydrogen bond between the main chain and dangling chains, thereby increasing molecular chain friction and energy dissipation. This work overcomes the challenge of balancing the damping and mechanical properties of polyurethane, providing a new strategy for designing high performance polyurethane damping elastomers. [ABSTRACT FROM AUTHOR]

Molecules in the bulk state are typically constrained by multiple intermolecular interactions, making it challenging to develop emission‐tunable solid‐state materials. Manipulating molecular motion is essential for achieving dynamic solid‐state emissions. Herein, various emission‐tunable 4CN@polymer films are developed whose multicolor luminescence arises from different molecular motion modes within the polymer microenvironments. There are three motion modes in the films: restricted, normal, and vigorous. In the normal mode, the film emits green light, shifting to purple under UV (515–387 nm). Cooling or fuming creates a rigid environment, leading to blue emission at 426 nm. High temperatures induce vigorous motion, causing quenched emission, which can be reactivated by cooling. This mechanism underscores the significant influence of molecular motion within flexible polymers on the luminescence behavior of 4CN@polymer films, enabling multicolor emission based on environmental conditions. The wide‐range fluorescence—from purple, blue, white, green, yellow‐green to dark—indicates promising applications in multifaceted dynamic displays and information security. This study offers novel perspectives on the correlation between solid‐state molecular motion and dynamic emission. [ABSTRACT FROM AUTHOR]

Small molecule organic materials have been considered promising candidates as cathodes in aqueous zinc‐ion batteries (AZIBs) because of their low cost, environmental friendliness, and sustainable production. However, the rapid capacity fading and sluggish kinetics restrict their practical applications, especially under extremely low temperatures (−50 °C). Here, by the condensation of hexaketocyclohexane octahydrate (HKCO) and 1, 2‐diaminoanthraquinone (DQ), a fully conjugated organic molecule, anthraquinone‐quinoxaline derivative (HATAN) is prepared. With the fully conjugated structure, HATAN possesses enhanced π‐electron delocalization and strong intermolecular interaction, which ensure superior electronic conductivity and physicochemical/electrochemical stability. Additionally, the introduction of multiple redox‐active sites (C═O and C═N) can increase the theoretical capacity of HATAN. Consequently, the HATAN cathode for AZIBs exhibits remarkable capacity, long lifespan, and high‐rate capability. Even at −50  C, an exceptional capacity of 75.4 mAh g−1 and 98% capacity retention over 1500 cycles can be preserved. This study presents valuable insights into the structure design of small molecule organic cathodes for advanced AZIBs which can efficiently operate at −50 °C. [ABSTRACT FROM AUTHOR]

Despite significant advancements in fabricating covalent organic frameworks (COFs) with diverse morphologies, creating COFs with superhelical nanostructures remains challenging. We report here the controlled synthesis of homochiral superhelical COF nanofibers by manipulating pendent alkyl chain lengths in organic linkers. This approach yields homochiral 3D COFs 13‐OR with a 10‐fold interpenetrated diamondoid structure (R=H, Me, Et, nPr, nBu) from enantiopure 1,1′‐bi‐2‐naphthol (BINOL)‐based tetraaldehydes and tetraamine. COF‐13‐OEt exhibits macroscopic chirality as right‐handed and left‐handed superhelical fibers, whereas others adopt spherical or non‐helical morphologies. Time‐tracking shows a self‐assembly process from non‐helical strands to single‐stranded helical fibers and intertwined superhelices. Ethoxyl substituents, being of optimal size, balance solvophobic effects and intermolecular interactions, driving the formation of superhelical nanostructures, with handedness determined by BINOL chirality. The superhelical nature of these materials is evident in their chiral recognition and spin‐filter properties, showing significantly improved enantiodiscrimination in carbohydrate binding (up to six times higher enantioselectivity) and a remarkable chiral‐induced spin selectivity (CISS) effect with a 48–51 % spin polarization ratio, a feature absent in non‐helical analogs. [ABSTRACT FROM AUTHOR]

Passivation of perovskite crystals is a crucial strategy to improve the efficiency and stability of perovskite solar cells (PSCs). Zwitterions, which contain both positive and negative charges in the molecule, can be used to passivate perovskite crystals. However, these materials strongly interact with each other, resulting in extremely low solubility in common organic solvents. The low solubility of zwitterions hinders the formation of uniform films, which negatively affects perovskite crystal growth. In this study, a liquid‐type zwitterion (LTZ) is synthesized by modulating intermolecular interactions of the zwitterion (3‐(1‐Pyridinio)‐1‐propanesulfonate). By suppressing intermolecular interactions, the solubility and processibility of the zwitterion in common organic solvents are successfully improved. The well‐distributed LTZ‐treated films are obtained, resulting in better electrical properties for the PSCs compared to solid‐type zwitterion‐based devices. With these characteristics, the resulting device achieves a power conversion efficiency of 24.9% with excellent thermal stability (under 60 °C and N2 atmosphere), maintaining over 80% of its initial efficiency for 1968 h. In addition, the PSC module (active area of 32.7 cm2) achieves an improved efficiency of 19.86% with high open‐circuit voltage and fill factor. The results suggest that interface engineering with an LTZ has the potential to fabricate efficient and stable PSCs. [ABSTRACT FROM AUTHOR]

Material design based on the assembly of functional units has demonstrated tremendous technical and commercial potential. Among others, polymers are identified to be an ideal building block due to their abundant functional groups, high programmability, and great biocompatibility. In this review, introducing recently developed advanced materials enabled by rationally designed polymer self‐assembly are focussed. The working principle of typical intermolecular interactions to shape nano‐patterns and structural heterogeneity is first explained in detail. Following that, methods to prepare advanced materials and their characteristic properties are discussed. The superior performance of polymer assemblies renders numerous potential applications in ultra‐tough devices, soft robotics, electronics, sensors, and biomedicine. A brief account of representative examples is highlighted and a perspective on this field is provided at the end. [ABSTRACT FROM AUTHOR]