Deciphering synergetic core-shell transformation from [Mo(6)O(22)@Ag(44)] to [Mo(8)O(28)@Ag(50)]

The structural transformation of high-nuclearity silver clusters from one to another induced by specific stimuli is of scientific significance in terms of both cluster synthesis and reactivity. Herein, we report two silver-thiolate clusters, [Mo(6)O(22)@Ag(44)] and [Mo(8)O(28)@Ag(50)], which are templated by isopolymolybdates inside and covered by (i)PrS(−) and PhCOO(−) ligands on the surfaces. Amazingly, the [Mo(8)O(28)@Ag(50)] can be transformed from [Mo(6)O(22)@Ag(44)] by adding PhCOOH which increases the degree of condensation of molybdates template from Mo(6)O(22)(8-) to Mo(8)O(28)(8-), then enlarging the outer silver shell from Ag(44) to Ag(50). The evolution of solution species revealed by time-dependent electrospray ionization mass spectrometry (ESI-MS) suggests a breakage-growth-reassembly (BGR) transformation mechanism. These results not only provide a combined assembly strategy (anion-template + induced transformation) for the synthesis of silver-thiolate clusters but also help us to better understand the complex transformation process underpinning the assembly system.