Eight　silver　(I)　complexes　with　P-donor　ligands　[triphenylphosphine　(PPh3),　bis(diphenylphosphino)　methane　(dppm),　1,2-bis(diphenylphosphino)ethane　(dppe)　and　1,4-bis(diphenylphosphino)butane　(dppb)]　and　mercaptan　ligands　[3-amino-5-mercapto-1,2,4-triazole　(H(2)AMTA),　2-amino-5-mercapto-1,3,4-thiadiazole　(HAMTD),　2-mercapto-6-nitrobenzothiazole　(HMNBT)　and　2-mercapto-5-methyl-benzimidazole　(HMMBD)]　named　by　[Ag-2(PPh3)(4)(HAMTA)(2)](n)　(1),　[Ag-3(dppm)(3)(AMTD)(2)](2)(BF4)(2)center　dot(dppm)　(2),　[Ag-3(dppm)(3)(AMTD)(2)](2)(ClO4)(2)center　dot(dppm)　(3),　[Ag-4(dppm)(4)(MNBT)(2)](SO4)center　dot(H2O)　(4),　[Ag-4(dppe)(4)　(HAMTA)(2)(AMTA)]　(5),　[Ag-2(dppb)(2)(HAMTD)(2)](CF3SO3)(2)center　dot　2(CH3OH)　(6),　[Ag-2(dppb)(2)(HMNBT)(2)](CF3SO3)(2)　(7)　and　{[Ag(dppb)(HMMBD)(2)](CF3SO3)center　dot　2(CH3OH)center　dot(H2O)}(n)　(8)　are　characterized　by　X-ray　diffraction,　NMR　and　fluorescence　spectroscopy.　Complexes　1　and　8　show　2D　network　structure.　Complexes　2-5　are　multi-nuclear　clusters.　Complexes　6-7　are　of　di-nuclear　structure.　In　complex　7,　the　offset　pi...pi　interactions　between　the　neighboring　benzene　rings　help　to　form　the　1-D　infinite　chain.　All　the　emission　peaks　of　these　complexes　are　attributed　to　ligands-centered　[pi-pi*]　transitions.　(C)　2017　Elsevier　Ltd.　All　rights　reserved.