Chiroptical Activity Amplification of Chiral Metal Nanoclusters via Surface/Interface Solidification.

ACS Nano

New Cornerstone Science Laboratory, State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and National and Local Joint Engineering Research Center of Preparation Technology of Nanomaterials, College of Chemistry and Chemical

Published: May 2024


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Article Abstract

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.4c01309DOI Listing

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