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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]

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]

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]

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]

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]

The structure of molecular aggregates is crucial for charge transport and photovoltaic performance in organic solar cells (OSCs). Herein, the intermolecular interactions and aggregated structures of nonfused‐ring electron acceptors (NFREAs) are precisely regulated through a halogen transposition strategy, resulting in a noteworthy transformation from a 2D‐layered structure to a 3D‐interconnected packing network. Based on the 3D electron transport pathway, the binary and ternary devices deliver outstanding power conversion efficiencies (PCEs) of 17.46 % and 18.24 %, respectively, marking the highest value for NFREA‐based OSCs. [ABSTRACT FROM AUTHOR]

Curiosity‐driven innovations on the design and synthesis of nonplanar polycyclic aromatic/heteroaromatic compounds with new molecular topologies unfold exciting opportunities for harnessing their intriguing supramolecular properties and thereby the development of novel functional organic materials. This work presents such an innovative synthetic concept of a bottom‐up molecular topology engineering through a unique orchestrated octuple C−H activation reaction, toward the rapid synthesis of a novel class of double heptagon‐incorporated nitrogen‐doped laterally‐fused polycyclic compounds with rarely reported wavy structural configuration. The profound impact of the molecular wavy structures of these compounds on their properties is manifested by weak and tunable solid‐state intermolecular interactions controlling the electronic properties of the materials, leading to reversibly switchable fluorochromism in the solid state and thin films with mechanical force and solvent vapors as external stimuli, thereby indicating their potential applicability in rewritable fluorescent optical recording media, security papers, mechanosensors, volatile organic compound (VOC) sensors etc. [ABSTRACT FROM AUTHOR]

Structurally ordered soft materials that respond to complementary stimuli are susceptible to control over their spatial and temporal morphostructural configurations by intersectional or combined effects such as gating, feedback, shape‐memory, or programming. In the absence of general and robust design and prediction strategies for their mechanical properties, at present, combined chemical and crystal engineering approaches could provide useful guidelines to identify effectors that determine both the magnitude and time of their response. Here, we capitalize on the purported ability of soft intermolecular interactions to instigate mechanical compliance by using halogenation to elicit both mechanical and photochemical activity of organic crystals. Starting from (E)‐1,4‐diphenylbut‐2‐ene‐1,4‐dione, whose crystals are brittle and photoinert, we use double and quadruple halogenation to introduce halogen‐bonded planes that become interfaces for molecular gliding, rendering the material mechanically and photochemically plastic. Fluorination diversifies the mechanical effects further, and crystals of the tetrafluoro derivative are not only elastic but also motile, displaying the rare photosalient effect. [ABSTRACT FROM AUTHOR]

This article presents trioxa[9]circulene (3) as a novel member of hetero[n]circulenes. Its synthesis began with the synthesis of dimethoxydioxa[8]helicene (5) and used dimethoxydiepoxycyclononatrinaphthalene (4) as a key intermediate, despite the condensation reaction predominantly yielding a 1,4‐addition byproduct. The structures and properties of 3–5 were extensively investigated using experimental and computational methods. Analysis of the crystal structures reveal elongation of the internal C−C bonds in the nine‐membered ring of 3 compared to 4 and 5. Computational studies demonstrate the remarkable flexibility of trioxa[9]circulene's saddle‐shaped polycyclic framework, while the other two compounds are rigid with large racemization barriers. Optically pure forms of 4 and 5 exhibit absorption and luminescence dissymmetry factors on the order of 10−2, with smaller values observed for compound 4. In the crystal structures, molecules of 3 stack to form columns with remarkable π–π overlap, and the π–π interactions of 4 exhibit short intermolecular C‐to‐C contacts. Consequently, the solution‐processed film of 4 functioned as a p‐type organic semiconductor in field effect transistors. [ABSTRACT FROM AUTHOR]

Organics are gaining significance as electrode materials due to their merits of multi‐electron reaction sites, flexible rearrangeable structures and redox reversibility. However, organics encounter finite electronic conductivity and inferior durability especially in organic electrolytes. To circumvent above barriers, we propose a novel design strategy, constructing conductive network structures with extended π–π superposition effect by manipulating intermolecular interaction. Tetralithium 1,4,5,8‐naphthalenetetracarboxylate (LNTC) interwoven by carbon nanotubes (CNTs) forms LNTC@CNTs composite firstly for Li‐ion storage, where multiple conjugated carboxyls contribute sufficient Li‐ion storage sites, the unique network feature enables electrolyte and charge mobility conveniently combining electron delocalization in π‐conjugated system, and the enhanced π–π superposition effect between LNTC and CNTs endows laudable structural robustness. Accordingly, LNTC@CNTs maintain an excellent Li‐ion storage capacity retention of 96.4 % after 400 cycles. Electrochemical experiments and theoretical simulations elucidate the fast reaction kinetics and reversible Li‐ion storage stability owing to the electron delocalization and π–π superposition effect, while conjugated carboxyls are reversibly rearranged into enolates during charging/discharging. Consequently, a dual‐ion battery combining this composite anode and expanded graphite cathode exhibits a peak specific capacity of 122 mAh g−1 and long cycling life with a capacity retention of 84.2 % after 900 cycles. [ABSTRACT FROM AUTHOR]

In the pursuit of highly efficient perovskite solar cells, spiro‐OMeTAD has demonstrated recorded power conversion efficiencies (PCEs), however, the stability issue remains one of the bottlenecks constraining its commercial development. In this study, we successfully synthesize a novel self‐polymerized spiro‐type interfacial molecule, termed v‐spiro. The linearly arranged molecule exhibits stronger intermolecular interactions and higher intrinsic hole mobility compared to spiro‐OMeTAD. Importantly, the vinyl groups in v‐spiro enable in situ polymerization, forming a polymeric protective layer on the perovskite film surface, which proves highly effective in suppressing moisture degradation and ion migration. Utilizing these advantages, poly‐v‐spiro‐based device achieves an outstanding efficiency of 24.54 %, with an enhanced open‐circuit voltage of 1.173 V and a fill factor of 81.11 %, owing to the reduced defect density, energy level alignment and efficient interfacial hole extraction. Furthermore, the operational stability of unencapsulated devices is significantly enhanced, maintaining initial efficiencies above 90 % even after 2000 hours under approximately 60 % humidity or 1250 hours under continuous AM 1.5G sunlight exposure. This work presents a comprehensive approach to achieving both high efficiency and long‐term stability in PSCs through innovative interfacial design. [ABSTRACT FROM AUTHOR]

The development of innovative triplet materials plays a significant role in various applications. Although effective tuning of triplet formation by intersystem crossing (ISC) has been well established in solution, the modulation of ISC processes in the solid state remains a challenge due to the presence of other exciton decay channels through intermolecular interactions. The cyclic structure of cycloparaphenylenes (CPPs) offers a unique platform to tune the intermolecular packing, which leads to controllable exciton dynamics in the solid state. Herein, by integrating an electron deficient coronene diimide (CDI) unit into the CPP framework, a donor‐acceptor type of conjugated macrocycle (CDI‐CPP) featuring intramolecular charge‐transfer (CT) interaction was designed and synthesized. Effective intermolecular CT interaction resulting from a slipped herringbone packing was confirmed by X‐ray crystallography. Transient spectroscopy studies showed that CDI‐CPP undergoes ISC in both solution and the film state, with triplet generation time constants of 4.5 ns and 238 ps, respectively. The rapid triplet formation through ISC in the film state can be ascribed to the cooperation between intra‐ and intermolecular charge‐transfer interactions. Our results highlight that intermolecular CT interaction has a pronounced effect on the ISC process in the solid state, and shed light on the use of the characteristic structure of CPPs to manipulate intermolecular CT interactions. [ABSTRACT FROM AUTHOR]

π–π interactions are among the most important intermolecular interactions in supramolecular systems. Here we determine experimentally a universal parameter for their strength that is simply based on the size of the interacting contact surfaces. Toward this goal we designed a new cyclophane based on terrylene bisimide (TBI) π‐walls connected by para‐xylylene spacer units. With its extended π‐surface this cyclophane proved to be an excellent and universal host for the complexation of π‐conjugated guests, including small and large polycyclic aromatic hydrocarbons (PAHs) as well as dye molecules. The observed binding constants range up to 108 M−1 and show a linear dependence on the 2D area size of the guest molecules. This correlation can be used for the prediction of binding constants and for the design of new host–guest systems based on the herewith derived universal Gibbs interaction energy parameter of 0.31 kJ/molÅ2 in chloroform. [ABSTRACT FROM AUTHOR]

Replacement of sp2‐hybridized carbon in polycyclic aromatic hydrocarbons (PAHs) by boron affords electron‐deficient π‐scaffolds due to the vacant pz‐orbital of three‐coordinate boron with the potential for pronounced electronic interactions with electron‐rich metal surfaces. Using a diboraperylene diborinic acid derivative as precursor and a controlled on‐surface non‐covalent synthesis approach, we report on a self‐assembled chiral supramolecular kagome network on an Ag(111) surface stabilized by intermolecular hydrogen‐bonding interactions at low temperature. Scanning tunneling microscopy (STM) and spectroscopy (STS) reveal a flat band at ca. 0.33 eV above the Fermi level which is localized at the molecule center, in good agreement with tight‐binding model calculations of flat bands characteristic for kagome lattices. [ABSTRACT FROM AUTHOR]

Fluorine side chain functionalization of non‐fullerene acceptors (NFAs) represents an effective strategy for enhancing the performance of organic solar cells (OSCs). However, a knowledge gap persists regarding the relationship between structural changes induced by fluorine functionalization and the resultant impact on device performance. In this work, varying amounts of fluorine atoms were introduced into the outer side chains of Y‐series NFAs to construct two acceptors named BTP‐F0 and BTP‐F5. Theoretical and experimental investigations reveal that side‐chain fluorination significantly increase the overall average electrostatic potential (ESP) and charge balance factor, thereby effectively improving the ESP‐induced intermolecular electrostatic interaction, and thus precisely tuning the molecular packing and bulk‐heterojunction morphology. Therefore, the BTP‐F5‐based OSC exhibited enhanced crystallinity, domain purity, reduced domain spacing, and optimized phase distribution in the vertical direction. This facilitates exciton diffusion, suppresses charge recombination, and improves charge extraction. Consequently, the promising power conversion efficiency (PCE) of 17.3 % and 19.2 % were achieved in BTP‐F5‐based binary and ternary devices, respectively, surpassing the PCE of 16.1 % for BTP‐F0‐based OSCs. This work establishes a structure‐performance relationship and demonstrates that fluorine functionalization of the outer side chains of Y‐series NFAs is a compelling strategy for achieving ideal phase separation for highly efficient OSCs. [ABSTRACT FROM AUTHOR]

Polar molecular crystals, with their densely stacked polar nonlinear optical (NLO) active units, are favored for their large second harmonic generation (SHG) responses and birefringence. However, their potential for practical applications as Infrared (IR) NLO materials has historically been underappreciated due to the weak inter‐molecular interaction forces that may compromise their physicochemical properties. In this study, we propose molecular crystals with polar molecular cages as a treasure‐house for the development of superior IR NLO materials and a representative system, binary chalcogenide molecular crystals, composed of [P4Sn] (n=3–9) polar molecular cages, is introduced. These crystals may not only achieve wide band gap, large SHG response, and birefringence in a single structure, but also exhibit favorable physicochemical properties. We subsequently obtained a polar molecular crystal, α‐P4S5, which demonstrated exceptional IR optical properties, including a strong SHG response (1.1×AGS), wide band gap (3.02 eV), large birefringence (0.134@2050 nm), and a broad transmission range (0.41–14.7 μm). Moreover, it showed excellent water resistance and hardness. These findings highlight the potential of polar molecular crystals as a promising platform for the development of high‐performance IR NLO materials. [ABSTRACT FROM AUTHOR]

Topological gels possess structures that are cross‐linked only via physical constraints; ideally, no attractive intermolecular interactions act between their components, which yields interesting physical properties. However, most reported previous topological gels were synthesized based on supramolecular interlocked structures such as polyrotaxane, for which attractive intermolecular interactions are essential. Here, we synthesize a water‐soluble "molecular net" (MN) with a large molecular weight and three‐dimensional network structure using poly(ethylene glycol). When a water‐soluble monomer (N‐isopropylacrylamide) is polymerized in the presence of the MNs, the extending polymer chains penetrates the MNs to form an ideal topological MN gel with no specific attractive interactions between its components. The MN gels show unique physical properties as well a significantly high degree of swelling and high extensibility due to slipping of the physical cross‐linking. We postulate this method to yield a new paradigm in gel science with unprecedented physical properties. [ABSTRACT FROM AUTHOR]

Morphological control of all‐polymer blends is quintessential yet challenging in fabricating high‐performance organic solar cells. Recently, solid additives (SAs) have been approved to be capable in tuning the morphology of polymer: small‐molecule blends improving the performance and stability of devices. Herein, three perhalogenated thiophenes, which are 3,4‐dibromo‐2,5‐diiodothiophene (SA‐T1), 2,5‐dibromo‐3,4‐diiodothiophene (SA‐T2), and 2,3‐dibromo‐4,5‐diiodothiophene (SA‐T3), were adopted as SAs to optimize the performance of all‐polymer organic solar cells (APSCs). For the blend of PM6 and PY‐IT, benefitting from the intermolecular interactions between perhalogenated thiophenes and polymers, the molecular packing properties could be finely regulated after introducing these SAs. In situ UV/Vis measurement revealed that these SAs could assist morphological character evolution in the all‐polymer blend, leading to their optimal morphologies. Compared to the as‐cast device of PM6 : PY‐IT, all SA‐treated binary devices displayed enhanced power conversion efficiencies of 17.4–18.3 % with obviously elevated short‐circuit current densities and fill factors. To our knowledge, the PCE of 18.3 % for SA‐T1‐treated binary ranks the highest among all binary APSCs to date. Meanwhile, the universality of SA‐T1 in other all‐polymer blends is demonstrated with unanimously improved device performance. This work provide a new pathway in realizing high‐performance APSCs. [ABSTRACT FROM AUTHOR]

Utilizing intermolecular hydrogen‐bonding interactions stands for an effective approach in advancing the efficiency and stability of small‐molecule acceptors (SMAs) for polymer solar cells. Herein, we synthesized three SMAs (Qo1, Qo2, and Qo3) using indeno[1,2‐b]quinoxalin‐11‐one (Qox) as the electron‐deficient group, with the incorporation of a methylation strategy. Through crystallographic analysis, it is observed that two Qox‐based methylated acceptors (Qo2 and Qo3) exhibit multiple hydrogen bond‐assisted 3D network transport structures, in contrast to the 2D transport structure observed in gem‐dichlorinated counterpart (Qo4). Notably, Qo2 exhibits multiple and stronger hydrogen‐bonding interactions compared with Qo3. Consequently, PM6 : Qo2 device realizes the highest power conversion efficiency (PCE) of 18.4 %, surpassing the efficiencies of devices based on Qo1 (15.8 %), Qo3 (16.7 %), and Qo4 (2.4 %). This remarkable PCE in PM6 : Qo2 device can be primarily ascribed to the enhanced donor‐acceptor miscibility, more favorable medium structure, and more efficient charge transfer and collection behavior. Moreover, the PM6 : Qo2 device demonstrates exceptional thermal stability, retaining 82.8 % of its initial PCE after undergoing annealing at 65 °C for 250 hours. Our research showcases that precise methylation, particularly targeting the formation of intermolecular hydrogen‐bonding interactions to tune crystal packing patterns, represents a promising strategy in the molecular design of efficient and stable SMAs. [ABSTRACT FROM AUTHOR]

Nanofibers are one of the most important morphologies of molecular self‐assemblies, the formation of which relies on the diverse intermolecular interactions of fibrous‐forming units. In the past decade, rapid advances have been made in the biomedical application of nanofibers, such as bioimaging and tumor treatment. An important topic to be focused on is not only the nanofiber formation mechanism but also where it forms, because different destinations could have different influences on cells and its formation could be triggered by unique stimuli in organelles. It is therefore necessary and timely to summarize the nanofibers assembled in organelles. This minireview discusses the formation mechanism, triggering strategies, and biomedical applications of nanofibers, which may facilitate the rational design of nanofibers, improve our understanding of the relationship between nanofiber properties and organelle characteristics, allow a comprehensive recognition of organelles affected by materials, and enhance the therapeutic efficiency of nanofibers. [ABSTRACT FROM AUTHOR]

Compared with Zn2+ storage, non‐metallic charge carrier with small hydrated size and light weight shows fast dehydration and diffusion kinetics for Zn‐organic batteries. Here we first report NH4+/H+ co‐storage in self‐assembled organic superstructures (OSs) by intermolecular interactions of p‐benzoquinone (BQ) and 2, 6‐diaminoanthraquinone (DQ) polymer through H‐bonding and π–π stacking. BQ‐DQ OSs exhibit exposed quadruple‐active carbonyl motifs and super electron delocalization routes, which are redox‐exclusively coupled with high‐kinetics NH4+/H+ but exclude sluggish and rigid Zn2+ ions. A unique 4e− NH4+/H+ co‐coordination mechanism is unravelled, giving BQ‐DQ cathode high capacity (299 mAh g−1 at 1 A g−1), large‐current tolerance (100 A g−1) and ultralong life (50,000 cycles). This strategy further boosts the capacity to 358 mAh g−1 by modulating redox‐active building units, giving new insights into ultra‐fast and stable NH4+/H+ storage in organic materials for better Zn batteries. [ABSTRACT FROM AUTHOR]

Developing polymers with high electrical conductivity (σ) after n‐doping is a great challenge for the advance of the field of organic thermoelectrics (OTEs). Herein, we report a series of thiazole imide‐based n‐type polymers by gradually increasing selenophene content in polymeric backbone. Thanks to the strong intramolecular noncovalent N⋅⋅⋅S interaction and enhanced intermolecular Se⋅⋅⋅Se interaction, with the increase of selenophene content, the polymers show gradually lowered LUMOs, more planar backbone, and improved film crystallinity versus the selenophene‐free analogue. Consequently, polymer PDTzSI−Se with the highest selenophene content achieves a champion σ of 164.0 S cm−1 and a power factor of 49.0 μW m−1 K−2 in the series when applied in OTEs after n‐doping. The σ value is the highest one for n‐type donor‐acceptor OTE materials reported to date. Our work indicates that selenophene substitution is a powerful strategy for developing high‐performance n‐type OTE materials and selenophene incorporated thiazole imides offer an excellent platform in enabling n‐type polymers with high backbone coplanarity, deep‐lying LUMO and enhanced mobility/conductivity. [ABSTRACT FROM AUTHOR]

Condensed films of functional luminophores dominated by the magnitude and dimensionality of the intermolecular interactions play important roles in sensing performance. However, controlling the molecular assembly and regulating photophysical properties remain challenging. In this study, a new luminophore, ortho‐PBI‐Au, was synthesized by anchoring a cyclometalated alkynyl‐gold(III) unit at the ortho‐position of perylene bisimide. An unprecedented T‐type packing model driven by weak Au‐π interaction and Au−H bonds was observed, laying foundation for striking properties of the luminophore. Controlled assembly of ortho‐PBI‐Au at the air‐water interface, realized using the classical Langmuir–Schaeffer technique, afforded the obtained luminescent films with different packing structures. With an optimized film, sensitive, selective, and rapid detection of a hazardous new psychoactive substance, phenylethylamine (PEA), was achieved. The detection limit, response time, and recovery time were <4 ppb, <1 s, and <5 s, respectively, surpassing the performance of the PEA sensors known thus far. The relationship between the characters of films and the sensing performance was systematically examined by grey relational analysis (GRA). The present study suggests that designing novel molecular aggregation with definite adlayer structure is a crucial strategy to enhance the sensing performance, which could be favorable for the film‐based fluorescent sensors. [ABSTRACT FROM AUTHOR]

An accurate detection of lung metastasis is of great significance for making better treatment choices and improving cancer prognosis, but remains a big challenge in clinical practice. In this study, we propose a reinventing strategy to develop a pH‐activatable near‐infrared (NIR) fluorescent nanoprobe, pulmonary metastasis tracer (denoted as PMT), based on assembly of NIR dye IR780 and calcium phosphate (CaP). By delicately tuning the intermolecular interactions during the assembly process and dye doping content, as well as the synthetic condition of probe, the fluorescence of PMT could be finely adjusted via the tumor acidity‐triggered disassembly. Notably, the selected PMT9 could sharply convert subtle pH variations into a distinct fluorescence signal to generate high fluorescence ON/OFF contrast, dramatically reducing the background signals. Benefiting from such preferable features, PMT9 is able to precisely identify not only the tumor sites in orthotopic lung cancer models but also the pulmonary metastases in mice with remarkable signal‐to‐background ratio (SBR). This study provides a unique strategy to turn shortcomings of traditional dye IR780 during in vivo imaging into advantages and further expand the application of fluorescent probe to image lung associated tumor lesions. [ABSTRACT FROM AUTHOR]

Developing molecular fluorophores with enhanced fluorescence in aggregate state for the second near‐infrared (NIR‐II) imaging is highly desirable but remains a tremendous challenge due to the lack of reliable design guidelines. Herein, we report an aromatic substituent strategy to construct highly bright NIR‐II J‐aggregates. Introduction of electron‐withdrawing substituents at 3,5‐aryl and meso positions of classic boron dipyrromethene (BODIPY) skeleton can promote slip‐stacked J‐type arrangement and further boost NIR‐II fluorescence of J‐aggregates via increased electrostatic repulsion and intermolecular hydrogen bond interaction. Notably, NOBDP‐NO2 with three nitro groups (−NO2) shows intense NIR‐II fluorescence at 1065 nm and high absolute quantum yield of 3.21 % in solid state, which can be successfully applied in bioimaging, high‐level encoding encryption, and information storage. Moreover, guided by this electron‐withdrawing substituent strategy, other skeletons (thieno‐fused BODIPY, aza‐BODIPY, and heptamethine cyanine) modified with −NO2 are converted into J‐type aggregates with enhanced NIR‐II fluorescence, showing great potential to convert aggregation caused emission quenching (ACQ) dyes into brilliant J‐aggregates. This study provides a universal method for construction of strong NIR‐II emissive J‐aggregates by rationally manipulating molecular packing and establishing relationships among molecular structures, intermolecular interactions, and fluorescence properties. [ABSTRACT FROM AUTHOR]

The active metal template (AMT) strategy is a powerful tool for the formation of mechanically interlocked molecules (MIMs) such as rotaxanes and catenanes, allowing the synthesis of a variety of MIMs, including π‐conjugated and multicomponent macrocycles. Cycloparaphenylene (CPP) is an emerging molecule characterized by its cyclic π‐conjugated structure and unique properties. Therefore, diverse modifications of CPPs are necessary for its wide application. However, most CPP modifications require early stage functionalization and the direct modification of CPPs is very limited. Herein, we report the synthesis of a catenane consisting of [9]CPP and a 2,2′‐bipyridine macrocycle as a new CPP analogue that contains a reliable synthetic scaffold enabling diverse and concise post‐modification. Following the AMT strategy, the [9]CPP‐bipyridine catenane was successfully synthesized through Ni‐mediated aryl‐aryl coupling. Catalytic C−H borylation/cross‐coupling and metal complexation of the bipyridine macrocycle moiety, an effective post‐functionalization method, were also demonstrated with the [9]CPP‐bipyridine catenane. Single‐crystal X‐ray structural analysis revealed that the [9]CPP‐bipyridine catenane forms a tridentated complex with an Ag ion inside the CPP ring. This interaction significantly enhances the phosphorescence lifetime through improved intermolecular interactions. [ABSTRACT FROM AUTHOR]

Viscosity is an extremely important property for ion transport and wettability of electrolytes. Easy access to viscosity values and a deep understanding of this property remain challenging yet critical to evaluating the electrolyte performance and tailoring electrolyte recipes with targeted properties. We proposed a screened overlapping method to efficiently compute the viscosity of lithium battery electrolytes by molecular dynamics simulations. The origin of electrolyte viscosity was further comprehensively probed. The viscosity of solvents exhibits a positive correlation with the binding energy between molecules, indicating viscosity is directly correlated to intermolecular interactions. Salts in electrolytes enlarge the viscosity significantly with increasing concentrations while diluents serve as the viscosity reducer, which is attributed to the varied binding strength from cation–anion and cation–solvent associations. This work develops an accurate and efficient method for computing the electrolyte viscosity and affords deep insight into viscosity at the molecular level, which exhibits the huge potential to accelerate advanced electrolyte design for next‐generation rechargeable batteries. [ABSTRACT FROM AUTHOR]

The current availability of multi‐resonance thermally activated delayed fluorescence (MR‐TADF) materials with excellent color purity and high device efficiency in the deep‐blue region is appealing. To address this issue in the emerged nitrogen/carbonyl MR‐TADF system, we propose a spiro‐lock strategy. By incorporating spiro functionalization into a concise molecular skeleton, a series of emitters (SFQ, SOQ, SSQ, and SSeQ) can enhance molecular rigidity, blue‐shift the emission peak, narrow the emission band, increase the photoluminescence quantum yield by over 92 %, and suppress intermolecular interactions in the film state. The referent CZQ without spiro structure has a more planar skeleton, and its bluer emission in the solution state redshifts over 40 nm with serious spectrum broadening and a low PLQY in the film state. As a result, SSQ achieves an external quantum efficiency of 25.5 % with a peak at 456 nm and a small full width at half maximum of 31 nm in a simple unsensitized device, significantly outperforming CZQ. This work discloses the importance of spiro‐junction in modulating deep‐blue MR‐TADF emitters. [ABSTRACT FROM AUTHOR]

Fine‐tuning the thermodynamic self‐assembly of molecules via volatile solid additives has emerged to be an effective way to construct high‐performance organic solar cells. Here, three‐dimensional structured solid molecules have been designed and applied to facilitate the formation of organized molecular assembly in the active layer. By means of systematic theory analyses and film‐morphology characterizations based on four solid candidates, we preselected the optimal one, 4‐fluoro‐N,N‐diphenylaniline (FPA), which possesses good volatility and strong charge polarization. The three‐dimensional solids can induce molecular packing in active layers via strong intermolecular interactions and subsequently provide sufficient space for the self‐reassembly of active layers during the thermodynamic transition process. Benefitting from the optimized morphology with improved charge transport and reduced energy disorder in the FPA‐processed devices, high efficiencies of over 19 % were achieved. The strategy of three‐dimensional additives inducing ordered self‐assembly structure represents a practical approach for rational morphology control in highly efficient devices, contributing to deeper insights into the structural design of efficient volatile solid additives. [ABSTRACT FROM AUTHOR]

The role‐exchanging concerted torsional motion of two hydrogen atoms in the homochiral dimer of trans‐1,2‐cyclohexanediol was characterized through a combination of broadband rotational spectroscopy and theoretical modeling. The results reveal that the concerted tunneling motion of the hydrogen atoms leads to the inversion of the sign of the dipole moment components along the a and b principal axes, due to the interchange motion that cooperatively breaks and reforms one intermolecular hydrogen bond. This motion is also coupled with two acceptor switching motions. The energy difference between the two ground vibrational states arising from this tunneling motion was determined to be 29.003(2) MHz. The corresponding wavefunctions suggest that the two hydrogen atoms are evenly delocalized on two equivalent potential wells, which differs from the heterochiral case where the hydrogen atoms are confined in separate wells, as the permutation‐inversion symmetry breaks down. This intriguing contrast in hydrogen‐atom behavior between homochiral and heterochiral environments could further illuminate our understanding of the role of chirality in intermolecular interactions and dynamics. [ABSTRACT FROM AUTHOR]

Acepleiadylene (APD), a nonbenzenoid isomer of pyrene, exhibits a unique charge‐separated character with a large molecular dipole and a small optical gap. However, APD has never been explored in optoelectronic materials to take advantage of these appealing properties. Here, we employ APD as a building block in organic semiconducting materials for the first time, and unravel the superiority of nonbenzenoid APD in electronic applications. We have synthesized an APD derivative (APD‐IID) with APD as the terminal donor moieties and isoindigo (IID) as the acceptor core. Theoretical and experimental investigations reveal that APD‐IID has an obvious charge‐separated structure and enhanced intermolecular interactions as compared with its pyrene‐based isomers. As a result, APD‐IID displays significantly higher hole mobilities than those of the pyrene‐based counterparts. These results imply the advantages of employing APD in semiconducting materials and great potential of nonbenzenoid polycyclic arenes for optoelectronic applications. [ABSTRACT FROM AUTHOR]

Stabilizing liquids based on supramolecular assembly (non‐covalent intermolecular interactions) has attracted significant interest, due to the increasing demand for soft, liquid‐based devices where the shape of the liquid is far from the equilibrium spherical shape. The components comprising these interfacial assemblies must have sufficient binding energies to the interface to prevent their ejection from the interface when the assemblies are compressed. Here, we highlight recent advances in structuring liquids based on non‐covalent intermolecular interactions. We describe some of the progress made that reveals structure–property relationships. In addition to treating advances, we discuss some of the limitations and provide a perspective on future directions to inspire further studies on structured liquids based on supramolecular assembly. [ABSTRACT FROM AUTHOR]

Solvothermal reaction of 5,5′‐(pyridine‐2,6‐diylbis(oxy))diisophthalic acid (H4L) with europium(III) or terbium(III) nitrates in acetonitrile‐water (1 : 1) at 120 °C gave rise to isostructural 2D coordination polymers, [Ln(HL)(H2O)3]∞ (NIIC‐1‐Eu and NIIC‐1‐Tb), the layers of which are composed by eight‐coordinated lanthanide(III) ions interconnected by triply deprotonated ligands HL3−. The layers are packed in the crystal without any specific intermolecular interactions between them, allowing the facile preparation of stable water suspensions, in which NIIC‐1‐Tb exhibited top‐performing sensing properties through luminescence quenching effect with exceptionally low detection limits towards Fe3+ (LOD 8.62 nM), ofloxacin (OFX) antibiotic (LOD 3.91 nM) and cotton phytotoxicant gossypol (LOD 2.27 nM). In addition to low detection limit and high selectivity, NIIC‐1‐Tb features fast sensing response (within 60–90 seconds), making it superior to other MOF‐based sensors for metal cations and organic toxicants. The photoluminescence quantum yield of NIIC‐1‐Tb was 93 %, one of the highest among lanthanide MOFs. Mixed‐metal coordination polymers NIIC‐1‐EuxTb1−x demonstrated efficient photoluminescence, the color of which could be modulated by the excitation wavelength and time delay for emission monitoring (within 1 millisecond). Furthermore, an original 2D QR‐coding scheme was designed for anti‐counterfeiting labeling of goods based on unique and tunable emission spectra of NIIC‐1‐Ln coordination polymers. [ABSTRACT FROM AUTHOR]

Reducing non‐radiative recombination energy loss (ΔE3) is one key to boosting the efficiency of organic solar cells. Although the recent studies have indicated that the Y‐series asymmetric acceptors‐based devices featured relatively low ΔE3, the understanding of the energy loss mechanism derived from molecular structure change is still lagging behind. Herein, two asymmetric acceptors named BTP‐Cl and BTP‐2Cl with different terminals were synthesized to make a clear comparative study with the symmetric acceptor BTP‐0Cl. Our results suggest that asymmetric acceptors exhibit a larger difference of electrostatic potential (ESP) in terminals and semi‐molecular dipole moment, which contributes to form a stronger π–π interaction. Besides, the experimental and theoretical studies reveal that a lower ESP‐induced intermolecular interaction can reduce the distribution of PM6 near the interface to enhance the built‐in potential and decrease the charge transfer state ratio for asymmetric acceptors. Therefore, the devices achieve a higher exciton dissociation efficiency and lower ΔE3. This work establishes a structure‐performance relationship and provides a new perspective to understand the state‐of‐the‐art asymmetric acceptors. [ABSTRACT FROM AUTHOR]

Designing multi‐resonance (MR) emitters that can simultaneously achieve narrowband emission and suppressed intermolecular interactions is challenging for realizing high color purity and stable blue organic light‐emitting diodes (OLEDs). Herein, a sterically shielded yet extremely rigid emitter based on a triptycene‐fused B,N core (Tp‐DABNA) is proposed to address the issue. Tp‐DABNA exhibits intense deep blue emissions with a narrow full width at half maximum (FWHM) and a high horizontal transition dipole ratio, superior to the well‐known bulky emitter, t‐DABNA. The rigid MR skeleton of Tp‐DABNA suppresses structural relaxation in the excited state, with reduced contributions from the medium‐ and high‐frequency vibrational modes to spectral broadening. The hyperfluorescence (HF) film composed of a sensitizer and Tp‐DABNA shows reduced Dexter energy transfer compared to those of t‐DABNA and DABNA‐1. Notably, deep blue TADF‐OLEDs with the Tp‐DABNA emitter display higher external quantum efficiencies (EQEmax=24.8 %) and narrower FWHMs (≤26 nm) than t‐DABNA‐based OLEDs (EQEmax=19.8 %). The HF‐OLEDs based on the Tp‐DABNA emitter further demonstrate improved performance with an EQEmax of 28.7 % and mitigated efficiency roll‐offs. [ABSTRACT FROM AUTHOR]

Colloidal supraparticles integrated with multicomponent primary particles come with emerging or synergetic functionalities. However, achieving the functional customization of supraparticles remains a great challenge because of the limited options of building blocks with tailorability and functional extensibility. Herein, we developed a universal approach to construct customizable supraparticles with desired properties from molecular building blocks obtained by the covalent conjugation of catechol groups with a series of orthogonal functional groups. These catechol‐terminated molecular building blocks can assemble into primary particles driven by various intermolecular interactions (i.e. metal‐organic coordination, host–guest, and hydrophobic interactions), and then further assemble into supraparticles governed by catechol‐mediated interfacial interactions. Our strategy enables the formation of supraparticles with diverse functionalities, such as dual‐pH responsiveness, light‐controllable permeability, and non‐invasive fluorescence labeling of living cells. The ease with which these supraparticles can be fabricated, and the ability to tailor their chemical and physical properties through the choice of metals and orthogonal functional groups used, should enable a variety of applications. [ABSTRACT FROM AUTHOR]

The engineering of intermolecular interaction is challenging but critical for magnetically switchable molecules. Here, we prepared two cyanide‐bridged [Fe4Co4] cube complexes via the alkynyl‐ and alcohol‐functionalized trispyrazoyl capping ligands. The alkynyl‐functionalized complex 1 exhibited a thermally‐induced incomplete metal‐to‐metal electron transfer (MMET) behaviour at around 220 K, while the mixed alkynyl/alcohol‐functionalized cube of 2 showed a complete and abrupt MMET behaviour at 232 K. Remarkably, both compounds showed a long‐lived photo‐induced metastable state up to 200 K. The crystallographic study demonstrated that the incomplete transition of 1 was likely due to the possible elastic frustration originating from the competition between the anion‐propagated elastic interactions and inter‐cluster alkynyl‐alkynyl & CH‐alkynyl interactions, whereas the latter are eliminated in 2 as a result of the partial substitution by the alcohol‐functionalized ligand. Additionally, the introduction of chemically distinguishable cobalt centers within the cube unit of 2 did not lead to a two‐step but a one‐step transition, possibly because of the strong ferroelastic intramolecular interaction through the cyanide bridges. [ABSTRACT FROM AUTHOR]

Aqueous redox flow batteries (ARFBs) are a promising technology for grid‐scale energy storage, however, their commercial success relies on redox‐active materials (RAM) with high electron storage capacity and cost competitiveness. Herein, a redox‐active material lithium ferrocyanide (Li4[Fe(CN)6]) is designed. Li+ ions not only greatly boost the solubility of [Fe(CN)6]4− to 2.32 M at room temperature due to weak intermolecular interactions, but also improves the electrochemical performance of [Fe(CN)6]4−/3−. By coupling with Zn, ZIRFBs were built, and the capacity of the batteries was as high as 61.64 Ah L−1 (pH‐neutral) and 56.28 Ah L−1 (alkaline) at a [Fe(CN)6]4− concentration of 2.30 M and 2.10 M. These represent unprecedentedly high [Fe(CN)6]4− concentrations and battery energy densities reported to date. Moreover, benefiting from the low cost of Li4[Fe(CN)6], the overall chemical cost of alkaline ZIRFB is as low as $11 per kWh, which is one‐twentieth that of the state‐of‐the‐art VFB ($211.54 per kWh). This work breaks through the limitations of traditional electrolyte composition optimization and will strongly promote the development of economical [Fe(CN)6]4−/3−‐based RFBs in the future. [ABSTRACT FROM AUTHOR]

NIR‐II‐emitting photosensitizers (PSs) have attracted great research interest due to their promising clinical applications in imaging‐guided photodynamic therapy (PDT). However, it is still challenging to realize highly efficient PDT on NIR‐II PSs. In this work, we develop a chlorination‐mediated π–π organizing strategy to improve the PDT of a PS with conjugation‐extended A‐D‐A architecture. The significant dipole moment of the carbon‐chlorine bond and the strong intermolecular interactions of chlorine atoms bring on compact π–π stacking in the chlorine‐substituted PS, which facilitates energy/charge transfer and promotes the photochemical reactions of PDT. Consequently, the resultant NIR‐II emitting PS exhibits a leading PDT performance with a yield of reactive oxygen species higher than that of previously reported long‐wavelength PSs. These findings will enlighten the future design of NIR‐II emitting PSs with enhanced PDT efficiency. [ABSTRACT FROM AUTHOR]

Phosphorescence of organic materials is highly dependent on intermolecular interactions, for the sensitive triplet excitons toward environment and aggregated structures. However, until now, relationship between phosphorescence and intermolecular interactions is still unclear for complicated influence factors and uncontrollable aggregated behaviors. Herein, taking temperature as the controlled variable, the afterglow can continuously change from blue to green, then to yellow, even achieve the white emission with deuteration process. It is mainly due to the hierarchical architectures of molecular aggregates with rational distribution of intermolecular interactions, as well as gradually unlocking process of interactions with different energies. Accordingly, the one‐to‐one correspondence between the determinate interactions and excited triplet states have been established, guiding accurate design of desirable phosphorescence materials by hierarchical control of aggregated structures. [ABSTRACT FROM AUTHOR]

Flexible metal‐organic materials are of growing interest owing to their ability to undergo reversible structural transformations under external stimuli. Here, we report flexible metal‐phenolic networks (MPNs) featuring stimuli‐responsive behavior to diverse solute guests. The competitive coordination of metal ions to phenolic ligands of multiple coordination sites and solute guests (e.g. glucose) primarily determines the responsive behavior of the MPNs, as revealed experimentally and computationally. Glucose molecules can be embedded into the dynamic MPNs upon mixing, leading to the reconfiguration of the metal‐organic networks and thus changes in their physicochemical properties for targeting applications. This study expands the library of stimuli‐responsive flexible metal‐organic materials and the understanding of intermolecular interactions between metal‐organic materials and solute guests, which is essential for the rational design of responsive materials for various applications. [ABSTRACT FROM AUTHOR]

Synthetic macrocycles have served as principal tools for supramolecular chemistry, have greatly extended the scope of organic charge transfer (CT) complexes, and have proved to be of great practical value in the solid state during the past few years. In this Minireview, we summarize the research progress on the macrocycle‐based crystalline supramolecular assemblies primarily driven by intermolecular CT interactions (a.k.a. macrocycle‐based crystalline CT assemblies, MCCAs for short), which are classified by their donor–acceptor (D‐A) constituent elements, including simplex macrocyclic hosts, heterogeneous macrocyclic hosts, and host–guest D‐A pairs. Particular attention will be focused on their diverse functions and applications, as well as the underlying CT mechanisms from the perspective of crystal engineering. Finally, the remaining challenges and prospects are outlined. [ABSTRACT FROM AUTHOR]

Without chiral induction the emergence of homochirality from achiral molecules is rather serendipitous, as the rationale is somewhat ambiguous. We herein provide a plausible solution. From achiral precursors are formed a pair of interconverting cage conformers that exhibit a C3‐axis as the only symmetry element. When their interconversion is impeded with intramolecular H‐bonding, each conformer self‐sorts into a homochiral crystal, which is driven by a helical network of multivalent intermolecular interactions during the self‐assembly of homochiral cage conformers. As no chiral induction is involved throughout, we believe our study could enlighten the rational design for the emergence of homochirality with several criteria: 1) formation of a molecule without inversion center or mirror plane; 2) suppression of the enantiomeric interconversion, and introduction of multivalent interactions along the helical trajectory of screw symmetry within the resulting superstructure. [ABSTRACT FROM AUTHOR]

The solvation shell is essential for the folding and function of proteins, but how it contributes to protein misfolding and aggregation has still to be elucidated. We show that the mobility of solvation shell H2O molecules influences the aggregation rate of the amyloid protein α‐synuclein (αSyn), a protein associated with Parkinson's disease. When the mobility of H2O within the solvation shell is reduced by the presence of NaCl, αSyn aggregation rate increases. Conversely, in the presence CsI the mobility of the solvation shell is increased and αSyn aggregation is reduced. Changing the solvent from H2O to D2O leads to increased aggregation rates, indicating a solvent driven effect. We show the increased aggregation rate is not directly due to a change in the structural conformations of αSyn, it is also influenced by a reduction in both the H2O mobility and αSyn mobility. We propose that reduced mobility of αSyn contributes to increased aggregation by promoting intermolecular interactions. [ABSTRACT FROM AUTHOR]

The development of photoinduced luminescent radicals with dynamic emission color is still challenging. Herein we report a novel molecular radical system (TBIQ) that shows photo‐controllable luminescence, leading to a wide range of ratiometric color changes via light excitation. The conjugated skeleton of TBIQ is decorated with steric‐demanding tertiary butyl groups that enable appropriate intermolecular interaction to make dynamic intermolecular coupling possible for controllable behaviors. We reveal that the helicenic pseudo‐planar conformation of TBIQ experiences a planarization process after light excitation, leading to more compactly stacked supermolecules and thus generating radicals via intermolecular charge transfer. The photo‐controllable luminescent radical system is employed for a high‐level information encryption application. This study may offer unique insight into molecular dynamic motion for optical manufacturing and broaden the scope of smart‐responsive materials for advanced applications. [ABSTRACT FROM AUTHOR]

Searching the cost‐effective organic semiconductors is strongly needed in order to facilitate the practice of organic solar cells (OSCs), yet to be fulfilled. Herein, we have succeeded in developing two non‐fused ring electron acceptors (NFREAs), leading to the highest efficiency of 16.2 % for the NFREA derived OSCs. These OSCs exhibit the superior operational stabilities under one sun equivalent illumination without ultraviolet (UV) filtration. It is revealed that the modulation of halogen substituents on aromatic side chains, as the new structural tool to tune the intermolecular interaction and optoelectronic properties of acceptors, not only promotes the interlocked tic‐tac‐toe frame of three‐dimensional stacks in solid, but also improves charge dynamics of acceptors to enable high‐performance and stable OSCs. [ABSTRACT FROM AUTHOR]