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A new ligand,2-(2-methoxynaphthyl)-1H-imidazo[4,5-f][1,10]phenanthroline (mnipH),was synthesized by the condensation of 2-methoxy-1-naphthaldehyde and 5,6-diamino-l,10-phenanthroline.Then three ionic copper(Ⅰ) complexes were obtained through the reactions of[Cu(MeCN)4]ClO4,mnipH and the chelating diphosphine ligands with a molar ratio of 1∶1∶1.The photoluminescence and the corresponding luminescent mechanism of all copper(Ⅰ) complexes in the solid state were investigated at room temperature.