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Reported herein is the facial synthesis, molecular structure, and catalysis of a Pt/Ag nanocluster costabilized by organic ligands of phosphines and inorganic ligands of chlorides. The nanocluster with molecular formula of [PtAg 18 (dppp) 6 Cl 8 ](SbF 6 ) 2 has been obtained facilely by the one pot method. The structure of the cluster could be anatomized as the stabilizaiton of PtAg 12 -centered icosahedral core by the metalloligand of dppp-Ag-Cl, in which Cl - not only caps the surface Ag atoms but also binds the core and surface motifs. Featuring eight free electrons in its structure, the cluster exhibits high stability. More interestingly, the exposure of surface metal sites endows the cluster with counterintutively  high catalytic activity in hydrogenation reactions.

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.