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An All‐Alkynyl Protected 74‐Nuclei Silver(I)–Copper(I)‐Oxo Nanocluster: Oxo‐Induced Hierarchical Bimetal Aggregation and Anisotropic Surface Ligand Orientation
Author(s) -
Yang Yang,
Jia Tao,
Han YingZi,
Nan ZiAng,
Yuan ShangFu,
Yang FengLei,
Sun Di
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201906538
Subject(s) - copper , crystallography , cluster (spacecraft) , ion , metal ions in aqueous solution , chemistry , metal , ligand (biochemistry) , molecule , materials science , organic chemistry , biochemistry , receptor , computer science , programming language
The hardness of oxo ions (O 2− ) means that coinage‐metal (Cu, Ag, Au) clusters supported by oxo ions (O 2− ) are rare. Herein, a novel μ 4 ‐oxo supported all‐alkynyl‐protected silver(I)–copper(I) nanocluster [Ag 74− x Cu x O 12 (PhC≡C) 50 ] ( NC‐1 , avg. x =37.9) is characterized. NC‐1 is the highest nuclearity silver–copper heterometallic cluster and contains an unprecedented twelve interstitial μ 4 ‐oxo ions. The oxo ions originate from the reduction of nitrate ions by NaBH 4 . The oxo ions induce the hierarchical aggregation of Cu I and Ag I ions in the cluster, forming the unique regioselective distribution of two different metal ions. The anisotropic ligand coverage on the surface is caused by the jigsaw‐puzzle‐like cluster packing incorporating rare intermolecular C−H⋅⋅⋅metal agostic interactions and solvent molecules. This work not only reveals a new category of high‐nuclearity coinage‐metal clusters but shows the special clustering effect of oxo ions in the assembly of coinage‐metal clusters.