Syntheses and structural studies of heterobimetallic thiocarboxylate complexes containing zinc and silver

Novel heterobimetallic complexes, [(PPh3)2Ag(μ-SCOth)2Zn(SCOth)(H2O)] (1) and {[(PPh3)2Ag(μ-SCOPh)2Zn(SCOPh)(H2O)][(PPh3)2Ag(μ-SCOPh)Zn(SCOPh)2]} (2) have been prepared and characterized by FTIR, 1H, 13C and 31P NMR spectroscopy. Molecular structures of the complexes have been determined by single crystal X-ray diffraction technique. In these complexes the two metal atoms (Ag and Zn) are held together by bridging (μ-S or μ-O,S) thiocaboxylate groups. The terminal thiocarboxylate ligand binds monodentately (through S) in 1. Structure of 2 is unique as two different molecules, [(PPh3)2Ag(μ-SCOPh)Zn(SCOPh)2] and [(PPh3)2Ag(μ-SCOPh)2Zn(SCOPh)H2O] co-crystallize in the same lattice. The terminal thiocarboxylate ligand is monodentate (S) in the latter while bidentate (O,S) in the former molecule. Electronic spectral behaviors of the complexes have been explained by TDDFT calculations. Luminescence properties of both have been studied in solid state.