Photoisomerization-modulated supramolecular chirality inversion and energy-transfer efficiency in a cyanostilbene-glutamide-based self-assembly system

Journal of Molecular Liquids, Journal Year: 2024, Volume and Issue: 409, P. 125477 - 125477

Published: July 9, 2024

Language: Английский

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Homochiral Covalent Organic Frameworks with Superhelical Nanostructures Enable Efficient Chirality‐Induced Spin Selectivity

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(51)

Published: Aug. 24, 2024

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

Language: Английский

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Transfer of Chirality in Complex Hybrid Materials for Chirality-Induced Spin Selectivity

Published: Jan. 1, 2024

Language: Английский

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Efficient Transfer of Chirality in Complex Hybrid Materials and Impact on Chirality-induced Spin Selectivity

Chemistry of Materials, Journal Year: 2024, Volume and Issue: 36(23), P. 11449 - 11461

Published: Nov. 20, 2024

Transfer of chirality, or transmission asymmetric information from one system to another, plays an essential role in fundamental biological and chemical processes and, therefore, is for life. This phenomenon also holds immense potential spintronics the context chirality-induced spin selectivity (CISS). In CISS, spatial arrangement chiral molecules influences state electrons during charge-transfer processes. chirality achiral material a hybrid environment enables induction polarization material, thus vastly expanding library CISS-active electronic materials. Such "induced" CISS signals could have different responses compared pure because properties come into play former case. addition, multiple sources can be used, which nontrivial contribution induced effect act either synergistically antagonistically. opens way achieving tunability via means. Earlier, such chirality-transfer resulting were demonstrated containing carbon nanotubes (CNTs) functionalized with agent (Fmoc-diphenylalanine l/d). this context, we extend result by investigating additional moiety (l-lysozyme enzyme crystals) system. Here, crystal surrounds chiral-functionalized CNTs, show that synergistic interactions more efficient transfer, changes effect. manifests form (a) stronger signal only single agent, (b) nonmonotonic temperature dependence sign reversal signal, (c) persistence at higher temperatures. Hybrid materials could, offer intricate control modification its constituents, not possible homogeneous systems sources.

Language: Английский

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Oxidation Triggered Supramolecular Chirality

Nano Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 9, 2024

Topochemical reactions normally occurring in the solid and crystalline state exhibit solvent-free catalyst-free properties, with high atom economy which have been widely applied materials science polymer synthesis. Herein, we explore potential of topochemical for controlling emergence supramolecular chirality precise fabrication chiroptical materials. Boronic acid pinacol esters (BPin) were conjugated to naphthalimides containing an inherent chiral cholesteryl group linked by alkyl or benzene spacers. The BPin segments oxidized H2O2 form hydroxyl groups, enhanced luminescence, reduced steric effects, increased amphiphilicity. liposomal aggregates underwent situ oxidation transformed into 1D nanoarchitectures, exhibiting macroscopic chirality, active Cotton circularly polarized luminescence. Oxidation could also initiate intimate interplay between building units guest molecule, evolution multiple component assembly system realized.

Language: Английский

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