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The origins of the chiroptical activities of inorganic nanostructures have perplexed scientists, and deracemization of high-nuclearity metal nanoclusters (NCs) remains challenging. Here, we report a single-crystal structure of Rac-Ag70 that contains enantiomeric pairs of 70-nuclearity silver clusters with 20 free valence electrons (Ag70), and each of these clusters is a doubly truncated tetrahedron with pseudo-T symmetry. A deracemization method using a chiral metal precursor not only stabilizes Ag70 in solution but also enables monitoring of the gradual enlargement of the electronic circular dichroism (CD) responses and anisotropy factor gabs. The chiral crystals of R/S-Ag70 in space group P21 containing a pseudo-T-symmetric enantiomeric NC show significant kernel-based and shell-based CD responses. The small symmetry breaking of Td symmetry arising from local distortion of Ag−S motifs and rotation of the apical Ag3 trigons results in large chiroptical responses. This work opens an avenue to construct chiral medium/large-sized NCs and nanoparticles, which are promising for asymmetric catalysis, nonlinear optics, chiral sensing, and biomedicine. Having control over the chirality of metal nanoclusters is challenging. Here, the authors report the deracemization of silver nanoclusters and monitor the chiroptical responses. [ABSTRACT FROM AUTHOR]

Using a carboxylic acid linker, this work achieved the epitaxially coordinated assembly of a Ag–S layer into a three-dimensional semi-conductive framework, with high thermal stability, as well as an interesting temperature-dependent luminescence response. This work provides a new avenue to prepare semi-conductive metal-chalcogenide layer-based materials in electricity-related applications. [ABSTRACT FROM AUTHOR]

Coinage metal (Au, Ag, Cu) cluster and polyoxometalate (POM) cluster represent two types of subnanometer “artificial atoms” with significant potential in catalysis, sensing, and nanomedicine. While composite clusters combining Ag/Cu clusters with POM have achieved considerable success, the assembly of gold clusters with POM is still lagging. Herein, we first designedly synthesized two cluster structural units: an Au3O cluster stabilized by diverse N‐heterocyclic carbene (NHC) ligands and an amine‐terminated POM linker. The subsequent reaction involved amine substitution in the POM linker for the central O atom in the Au3O cluster, resulting in the first ternary composite cluster—a POM cluster sandwiched by two Au clusters protected by NHCs. Single‐crystal X‐ray diffraction and other characteristic methods characterized their atomically precise structures. Furthermore, altering the NHC ligands decreased the number of gold atoms in the sandwich structures, accompanying the different protonated degrees of amine ligand in the terminal end of the POM linker. These composite clusters showed excellent performances in catalytic H2O2 conversion through the synergistic effect between gold clusters and POM clusters. This work opens a new avenue to functional composite metal clusters and would promote their enhanced catalysis applications through intercluster synergistic interactions within composite systems. [ABSTRACT FROM AUTHOR]