Direct　reactions　under　ambient　conditions　among　copper/silver　salts,　diimine　ligands　and　diphosphine　ligands　were　carried　out　at　different　rations,　generating　nine　novel　Cu(I)/Ag(I)　complexes,　[Cu(Dpq)　(dppP)](ClO4)　(1),　[Cu(DPPz)(dPPP)1(ClO4)　(2),　[Cu(Dpq)(POP)](ClO4)　(3),　[Cu(Dppz)(POP)](ClO4)　(4),　[Cu　(Dpq)(xantphos)](ClO4).0.843CH(2)Cl(2)　(5),　[Cu(Dppz)(xantphos)](ClO4)center　dot　2CH(2)Cl(2)　(6),　[Ag(Dpq)(xantphos)]　(ClO4)　(7),　[Ag(Dpq)(xantphos)](CF3SO)(3)　(8),　[Ag(Dpq)(POP)1(CF3SO3)　(9).　(Dpq　=　pyrazino[2,3-f][1,10]　phenanthroline,　Dppz　=　dipyrido[3,2-a:2＇,3＇-clphenazine,　POP　=　1,1＇-[(Oxydi-2,1-phenylene)]bis[1,1-diphenylphosphine],　xantphos　=　9,9-dimethyl-4,5-bis(diphenylphosphanyl)xanthene,　dppp　=　1,3-bis　(diphenylphosphine)propane).　Their　crystal　structures　have　been　determined　by　single　crystal　X-ray　diffraction　and　they　were　characterized　by　IR,　UV,　elemental　analysis,　fluorescence　spectra,　H-1　NMR　and　P-31　NMR　spectroscopy.　All　above　nine　Cu(I)/Ag(I)　complexes　have　intriguing　crystal　stacking　structures.　Complexes　3,　9　are　of　1D　infinite　chain　structures　formed　by　C-H　center　dot　center　dot　center　dot　pi　interactions　between　each　adjacent　molecule　while　complexes　1,　2,　5,　6,　8　are　of　2D　network　structures　because　of　hydrogen　bonds,　C-H　center　dot　center　dot　center　dot　pi　interactions　and　pi　center　dot　center　dot　center　dot　pi　interactions.　However,　complex　4　is　complicated　three-dimensional　structure　formed　by　C-H　center　dot　center　dot　center　dot　pi　interactions.　Some　of　the　complexes　exhibit　obvious　luminescence　in　the　solid　state,　and　interesting　photoluminescence　phenomenon　are　explained　in　detail.　Among　these　six　Cu(I)　complexes,　complex　5　shows　the　highest　quantum　yield　up　to　17.2%,　which　is　due　to　the　large　steric　hindrance　of　xantphos　ligand.　For　these　three　Ag(I)　complexes,　complex　8　displays　the　highest　quantum　yield　of　19.5%.　In　addition,　the　terahertz　time-domain　spectrum　(THz-TDS)　of　these　complexes　has　been　investigated　in　detail　leading　to　the　preliminary　discovery　of　correlation　between　terahertz　spectra　and　crystal　packing　of　complexes.　(C)　2019　Elsevier　Ltd.　All　rights　reserved.