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J Am Chem Soc. 2014 Jul 9;136(27):9532-5. doi: 10.1021/ja5025113. Epub 2014 Jun 30.

Metallophilicity-driven dynamic aggregation of a phosphorescent gold(I)-silver(I) cluster prepared by solution-based and mechanochemical approaches.

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  • 1Department of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University , Guangdong 515063, PR China.


We observed an unusual reversible aggregation process showing stimuli-responsive structural dynamics and optical changes attributed to the formation of a sandwich-like Au3-Ag-Au3 cluster, which can be synthesized through both solution and mechanochemical methods. Unlike many other heteronuclear gold-silver clusters, the affinity of two cyclic Au3 complexes and a Ag(I) ion is solely bound by ligand unsupported Au-Ag 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-liquid extraction is demonstrated, showing the uniqueness of this labile Au-Ag metallophilicity and hinting at the possibility of manipulating a bonding process through a heterogeneous route.

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