Synthesis and structural characterization of zinc(II) and cadmium(II) complexes with 2-oxo-1,3-dithiole-4,5-dithiolate and 1,10-phenanthroline

Isomorphous complexes Zn(dmid)(phen)2 (1) and Cd(dmid)(phen)2 (2) have been synthesized through a ligand substitute reaction. Their structures and properties have been characterized by elemental analysis, IR, UV–Vis, fluorescence and single-crystal X-ray analysis. The octahedral N4S2 coordination geometry, bonding, electronic structure and IR spectra of the Zn(dmid)(phen)2 molecule were studied in detail using DFT and INDO/S methods. In the crystal packing, there exists a strong <f>π–π</f> interaction between two parallel 1,10-phenanthrolines of adjacent molecules. Complex 1 (or 2) in the solid state exhibits an intensive fluorescence band at 539.5 nm (or 536 nm) when the excitation wavelength is 371 nm (or 370.5 nm) at room temperature. [Copyright &y& Elsevier]