Influence of ligand environment on the structure and properties of silver(i) dithiocarbamate cluster-based coordination polymers and dimersElectronic supplementary information (ESI) available: ORTEP diagram of 2 and 3, 31P NMR spectra of complexes 3 and 4, bond lengths (Å) and angles (°) for complexes 3 and 4, photophysical data of complexes, TGA results for the complexes (2, 4). CCDC 934751 (1), 934752 (2), 989805 (3) and 934753 (4). For ESI and crystallographic data in CIF or other electronic

Luminescent silver( i ) homo- and heteroleptic pyridyl functionalised dithiocarbamate (dtc) complexes of the form, [{Ag(L)} 4 ] ∞ (L = N -benzyl- N -methylpyridyldtc (L1) 1 , bis-( N -methylpyridyl)dtc (L2) 2 ) and [Ag(L)PPh 3 ] 2 (L = L1 ( 3 ), L2 ( 4 )) have been synthesized and characterized by elemental analysis, TGA, spectroscopy (IR, 1 H, 13 C and 31 P NMR and UV-Vis) and X-ray crystallography. Complexes 1 and 2 are isomorphous and have a tetranuclear cluster-based coordination polymeric structure. In these tetranuclear silver( i ) cluster subunits the four Ag atoms form a distorted tetrahedron. Complexes 3 and 4 are also isostructural and have centrosymmetric structures in which each Ag atom forms a distorted tetrahedral coordination geometry. All complexes are weakly conducting and exhibit semiconductor behaviour. 1-4 are strongly luminescent in solid phase; a correlation between their structure and luminescent properties has been established. Four silver dithiocarbamate complexes have been synthesized and characterized by microanalysis. 1 and 2 are tetranuclear cluster-based coordination polymers whereas 3 and 4 are dinuclear. All complexes are strongly luminescent in solid phase.