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In this work,three stable dumbbell-shaped silver clusters 1 ～3,formed by a novel bifunctional ligand Ph2P-C6H4-3-C--CH,are presented.All three complexes have cage structures constructed with thirty-six silver atoms,which are templated by chloride anions.During the self-assembly process of silver acetylides,argentophilic interactions and Ag(Ⅰ)-ethynide interactions are important for the formation of silver cores to yield a diversity of silver clusters.Weak molecular interactions (π-π,C-H· π,C-H…F,C-H…O) are also found in these complexes,which are crucial to stabilizing these silver clusters.Compared with simple alkynyl ligands (RC≡C-),the introduction of phosphine groups into alkynyl ligand can effectively control the undesired infinite growth of silver acetylides.The photophysical behaviors of complexes 1 ～3 are studied,showing intense orange roomtemperature luminescence in the solid state upon the exposure to UV light.The luminescence mainly arises from ligand-to-metal charge transfer (LMCT) and metal-cluster-centered transitions (MC) within the silver clusters.