Using polyhedral oligomeric silsesquioxane (POSS) modified by a thiol group as a protected ligand, atom-precise multi-heteorocluster-based dendrimers Ag @POSS (1 a and 1 b) were assembled. Through the reactive -SH groups, six POSS shell ligands stabilize the central 12-core silver(I) cluster by diverse Ag-S interactions. When such Ag @POSS complex was stimulated by different solvents (acetone or tetrahydrofuran), the core Ag silver(I) cluster underwent reversible structural transformation between flattened cubo-octahedral (in 1 a) and normal cubo-octahedral (in 1 b); concomitantly shell POSS clusters rearranged from pseudo-octahedral to quasi-octahedral. Furthermore, the film matrix modified by 1 a or 1 b showed different hydrophobicity.
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