“…Polyhedral oligomeric silsesquioxane (POSS) denotes ac lass of small silica nanclusters/nanoparticles with ar igid cage-like RSiO 1.5 conformation featuring attractive thermal and mechanical properties. [7][8][9][10] Thereadily tunable peripheral groups facilitate the rigid POSS as building blocks for the formation of high-ordered structures driven by intermolecular interactions such as hydrogen bonding [11] and metal coordination [12] to assemble coordination polymers.Recently, by coordination of thiol À POSS ligand with Cu I complex, anovel structure-defined 3D complex containing tetranuclear copper(I) cluster as secondary building unit has been demonstrated, [12b] indicating that the thiolÀPOSS is aversatile candidate in the design of metal cluster compounds.Inspired by this,w ec onsider that the thiol-POSS can be used as protecting shell ligands to induce the formation of new silver(I)-POSS cluster compounds, [13,14] which have never been reported. On the one hand, the designed Ag 12 @POSS 6 multiple heteoroclusters may combine the physicochemical properties ascribed to silver(I) cluster and POSS components, which forms anew family of cluster@clusters multifunctional compounds.O nt he other hand, if the silver(I) cluster is protected by cage POSS ligands,the steric hindrance between neighboring shell POSS ligands allows more small auxiliary ligands,such as solvent ligands and counter anion of silver(I) salt, to coordinate to the central silver(I) core.Asaresult, the auxiliary ligands induced silver(I) core transformation may be observed.…”