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It remains a grand challenge to amplify the chiroptical activity of chiral metal nanoclusters (NCs) although it is desirable for fundamental research and practical application. Herein, we report a strategy of surface/interface solidification (SIS) for enhancing the chiroptical activity of gold NCs. Structural analysis of [Au(2,4/2,4-BDPP)Cl] (BDPP is 2,4-bis(diphenylphosphino)pentane) clusters reveals that one of the interfacial gold atoms is flexible between two sites and large space is present on the surface, thus hampering chirality transfer from surface chiral ligands to metal core and leading to low chiroptical activity. Following SIS by filling the flexible sites and replacing chlorides with thiolate ligands affords another pair of [Au(2,4/2,4-BDPP)(4-F-CHS)], which shows a more compact and organized structure and thus an almost 40-fold enhancement of chiroptical activity. This work not only provides an efficient approach for amplifying the chiroptical activity of metal nanoclusters but also highlights the significance of achiral components in shaping chiral nanostructures.
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http://dx.doi.org/10.1021/acsnano.4c01309 | DOI Listing |
J Colloid Interface Sci
September 2025
Department of Advanced Materials Engineering for Information & Electronics, Kyung Hee University, Gyeonggi-do 17104, Republic of Korea. Electronic address:
We present a supramolecular templating strategy for inducing chirality in hybrid perovskites via confined crystallization within chiral super spaces-nanoconfined, helically ordered cavities formed by the self-assembly of achiral bent-core molecules with chiral additives. Upon removal of the additives, the resulting porous films retain permanent chirality. Quasi-2D hybrid organic-inorganic perovskites crystallized within these templates exhibit distinct chiroptical activity, including mirror-image circular dichroism and circularly polarized light emitting (CPLE), with CPLE dissymmetry factors reaching up to 1.
View Article and Find Full Text PDFOrg Lett
September 2025
Max Planck Institute of Microstructure Physics, Weinberg 2, 06120 Halle, Germany.
Helical nanographenes (NGs) play a crucial role in the development of chiral nanomaterials due to their distinctive optoelectronic and chiroptical properties. Herein, we report the efficient synthesis of two unprecedented azulene-embedded asymmetric triple helical NGs ( and ) with controllable helicene subunit lengths and π-extension. The crystallographic analysis confirms their highly twisted and asymmetric geometries.
View Article and Find Full Text PDFAdv Mater
September 2025
Department of Chemical Engineering, University of Michigan, Ann Arbor, MI, 48109, USA.
Metal-halide perovskites are known for their strong and tunable luminescence. However, the synthesis of perovskite-based particles with circularly polarized light emission (CPLE) remains challenging due to the complex interplay of metal-ligand chemistries, crystallization patterns, and chirality transfer mechanisms. Achiral perovskites can be deposited on chiral "hedgehog" particles (CHIPs) with twisted spikes, producing chiroptically active materials with spectroscopic bands specific to the perovskite and chirality specific to the template CHIPs.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2025
State Key Laboratory of Functional Crystals and Devices, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, P.R. China.
Chiral metal halide perovskites (CMHPs) are a promising class of chiroptical materials with significant potential applications in chiral-optoelectronic and chiral-spintronic devices. However, their chirality induction generally stems from the incorporation of chiral ligands, which constitutes compositional diversity and functional versatility. Herein, we report a significant chiral expression resulting from two distinct mechanisms: chirality transfer induced by chiral organic cations and mirror symmetry breaking driven by stereochemically active lone pairs, both contributing to controlled chirality induction.
View Article and Find Full Text PDFNanoscale
September 2025
IGCME, PCFM Lab, School of Chemistry, Sun Yat-Sen University, Guangzhou, 510275, China.
Spherical chiral polyrotaxanes (CPRs) with steerable circularly polarized luminescence (CPL) are intriguing as advanced chiroptical materials but have not been reported to date. Here, we constructed spherical chiral polyrotaxane (CPR) materials with steerable CPL by utilizing cyclodextrins (α-, β-, or γ-CyD) as the chiral wheel. Importantly, the structure and the CPL performance of the CPR materials can be regulated by varying the feeding amount and the type of cyclodextrin (α-, β-, or γ-CyD).
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