Compact accumulation of superatomic silver nanoclusters with an octahedral Ag 6 core ligated by trithiane.

Two superatomic solids, a bi-cluster compound, [Ag 6 (3S) 4 (OTf) 4 ][Ag 6 (3S) 4 (CC t Bu) 4 ](OTf) 2 [Ag6(0)·Ag6(i)], and a homologous nanocluster, [Ag 6 (3S) 4 (tfa) 4 ] (Ag6), have been described here, which are both close-packed in the crystal lattice with the ligation of trithiane. Their aggregation-state-dependent absorption and fluorescence properties could be ascribed to the enhanced intercluster charge-transfer in the crystalline state.