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A Homoleptic Alkynyl‐Ligated [Au 13 Ag 16 L 24 ] 3− Cluster as a Catalytically Active Eight‐Electron Superatom
Author(s) -
Qin Zhaoxian,
Sharma Sachil,
Wan Chongqing,
Malola Sami,
Xu Wenwu,
Häkkinen Hannu,
Li Gao
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202011780
Subject(s) - superatom , chemistry , homoleptic , alkyne , crystallography , cluster (spacecraft) , phenylacetylene , metal , catalysis , bimetallic strip , photochemistry , electronic structure , computational chemistry , organic chemistry , computer science , programming language
A new alkynylated cluster [Au 13 Ag 16 (C 10 H 6 NO) 24 ] 3− is prepared by a NaBH 4 mediated reduction method. The AuAg clusters are confirmed by sophisticated characterization techniques. It has a unique “Au center @Ag 12 @Au 12 Ag 4 ” metal framework which is protected by 24 atypical alkyne ligands L (L=C 10 H 6 NO). The ligands construct a unique type of motif L‐(Ag)‐Au‐(Ag)‐L at the cluster interface, where the alkyne (C≡C) group of each L was linked by sharing an Au atom through the σ bonds and each C≡C group was discretely connected to a chemically different Ag atom (Ag icosahedral /Ag cap ) through π bonds. The electronic and optical properties of [Au 13 Ag 16 L 24 ] 3− were studied. DFT characterized the cluster as a clear 8‐electron superatom, and peaks in the optical absorption spectrum were interpreted in terms of the P and D superatom states. The supported Au 13 Ag 16 L 24 /CeO 2 catalyst exhibited high catalytic activity and selectivity towards the A 3 ‐coupling reaction involving benzaldehyde, diethylamine, and phenylacetylene.