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The reaction of a K4[{Re6Si8}(OH)a6]·8H2O rhenium cluster salt with 4,4′‐bipyridine (bpy) or 4‐aminopyridine (apy) in an aqueous solution at mild temperature and pressure conditions lead to cluster functionalization and to the formation of two new compounds [{Re6Si8}(OH)a2(bpy)a4]·bpy·4H2O (1) and [{Re6Si8}(OH)a2(apy)a4]·2apy·2H2O (2). Their crystal structures are built up from trans‐[{Re6Si8}(OH)...
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