Metallophilicity-Driven Dynamic Aggregation of a Phosphorescent Gold(I)鈥揝ilver(I) Cluster Prepared by Solution-Based and Mechanochemical Approaches

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• 作者：Wen-Xiu Ni ; Yu-Min Qiu ; Mian Li ; Ji Zheng ; Raymond Wai-Yin Sun ; Shun-Ze Zhan ; Seik Weng Ng ; Dan Li
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：July 9, 2014
• 年：2014
• 卷：136
• 期：27
• 页码：9532-9535
• 全文大小：299K
• ISSN：1520-5126

文摘

We observed an unusual reversible aggregation process showing stimuli-responsive structural dynamics and optical changes attributed to the formation of a sandwich-like Au₃鈥揂g鈥揂u₃ cluster, which can be synthesized through both solution and mechanochemical methods. Unlike many other heteronuclear gold鈥搒ilver clusters, the affinity of two cyclic Au₃ complexes and a Ag^I ion is solely bound by ligand unsupported Au鈥揂g bonding. The assembly/disassembly behavior, further forming nanoaggregates, is controllable by adjusting the concentration of the solution. In the solid state, the insertion of Ag^I ion can be implemented through a mechanochemical approach, accompanied by visual color changes and reversible luminochromism. Furthermore, an uncommon solid鈥搇iquid extraction is demonstrated, showing the uniqueness of this labile Au鈥揂g metallophilicity and hinting at the possibility of manipulating a bonding process through a heterogeneous route.