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Using polyhedral oligomeric silsesquioxane (POSS) modified by a thiol group as a protected ligand, atom‐precise multi‐heteorocluster‐based dendrimers Ag12@POSS6 (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 Ag12@POSS6 complex was stimulated by different solvents (acetone...
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