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

Anionic zinc(II) complexes, [Zn(SCOR)3]− [R = th (1)] have been used for the synthesis of heterobimetallic complexes, [(PPh3)Cu(μ-SCOR)3Zn(PPh3)] [R = Ph (2) and th (3)]. All the three complexes have been characterized by FTIR, 1H and 13C NMR spectroscopy. The synthetic reactions involved phosphine migration from Cu(I) to Zn(II) in the cases of 2 and 3. Molecular structures of the complexes have been determined by single crystal X-ray diffraction and the structural features have been explained on the basis of NBO calculations. The Cu–Zn distance in these molecules are shorter than the sum of their covalent radii indicating the existence of a bond between the metals. Electronic spectral behavior of the complexes have been explained by TDDFT calculations. Luminescence properties of 3 has also been studied in solid state.