Cluster-Cracking Reaction, A New Method To Synthesize Unsymmetrical Dithiolate Complexes For The Study Of Third-Order Nonlinear Optical Properties

A new cluster-cracking method to synthesize dithiolate metal complexes was reported and four unsymmetric complexes with formula (Me4N)(2)[M(Ln)(SPh)(2)] (M = Cd and Zn, L1 = dmit = 1, 3-dithiole-2-thione-4, 5-dithiolate, L2 = dmid = 1, 3-dithiole-2-one-4, 5-dithiolate, SPh = thiophenolate) (1-4) were characterized by, elemental analysis, ER, UV NMR spectra and so on. The advantages of this method am summarized in two aspects: (1) the preparation is very convenient; (2) the reaction usually completed giving the product with high,purity. The crystal structure of 1 showed that the bond distances of Cd(II) to the sulfur of the thiophenolate group are shorter than those of Cd(II) to the sulfur of dmit, so that the thiophenolate group does not be replaced in the reaction and the mixed ligand complexes are the dominant products. The dmit complexes showed well third-order NLO properties, but not of the dmid complexes, although druid is an analogue to dmit.