Combinatorial Identification of Hydrides in a Ligated Ag40 Nanocluster with Non-compact Metal Core
Yuan, X., Sun, C., Li, X., Malola, S., Boon, K. T., Häkkinen, H., Zheng, L.-S., & Zheng, N. (2019). Combinatorial Identification of Hydrides in a Ligated Ag40 Nanocluster with Non-compact Metal Core. Journal of the American Chemical Society, 141(30), 11905-11911. https://doi.org/10.1021/jacs.9b03009
Published inJournal of the American Chemical Society
© 2019 American Chemical Society
No formation of bulk silver hydride has been reported. Until very recently, only few silver nanoclusters containing hydrides have been successfully prepared. However, due to the lack of effective techniques and also poor stability of hydride-containing Ag nanoclusters, the identification of hydrides’ location within Ag nanoclusters is challenging and not yet achieved although some successes have been reported on clusters of several Ag atoms. In this work, we report a detailed structural and spectroscopic characterization of the [Ag40(DMBT)24(PPh3)8H12]2+ (Ag40H12) cluster (DMBT=2,4-dimethylbenzenethiol). The metal framework consists of three-concentric shells of Ag8@Ag24@Ag8 which can be described as (ν1-cube)@(truncated-ν3-octahedron)@(ν2-cube), respectively. The presence of twelve hydrides in each cluster was systematically identified by various techniques. Based on a detailed analysis of the structural features and 1H and 2H NMR spectra, the positions of the 12 hydrides were determined to be residing on the 12 edges of the cubic core. As a result, the electron count of the Ag40 cluster is a two-electron superatomic system instead of a fourteen-electron system. Moreover, based on our DFT calculations and experimental probes, it was demonstrated that the 12 hydrides play a crucial role in stabilizing both the electronic and geometric structure of the Ag40H12 cluster. The successful synthesis of stable hydride-containing Ag nanoclusters and the identification of hydride positions are expected to simulate research attention on both synthesis and application of hydride-containing Ag nanomaterials ...
PublisherAmerican Chemical Society
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Related funder(s)Academy of Finland
Funding program(s)Research costs of Academy Professor, AoF
Additional information about fundingWe acknowledge the support from the National Key R&D Program of China (2017YFA0207302), the National Natural Science Foundation of China (21890752, 21731005, 21420102001, and 21721001), the fundamental research funds for central universities (20720180026). The work in University of Jyväskylä was supported by the Academy of Finland (HH’s Academy Professorship and grants 294217 and 319208). The computations were made at the CSC computing center in Espoo, Finland. HH acknowledges support from China’s National Innovation and Intelligence Introduction Base visitor program ...
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