Mixed-ligand Pt(II) dithione-dithiolato complexes: influence of the dicyanobenzodithiolato ligand on the second-order-NLO properties

The mixed-ligand dithiolene complex [Pt(Bz2pipdt)(dcbdt)] (1) bearing the two ligands Bz2pipdt = 1,4-dibenzyl-piperazine-3,2-dithione and dcbdt = dicyanobenzodithiolato, has been synthesized, characterized and studied to evaluate its second-order optical nonlinearity. The dithione/dithiolato character of the two ligands gives rise to an asymmetric distribution of the charge in the molecule. This is reflected by structural data showing that in the C2S2PtS2C2 dithiolene core the four sulfur atoms define a square-planar coordination environment of the metal where the Pt–S bond distances involving the two ligands are similar, while the C–S bond distances in the C2S2 units exhibit a significant difference in Bz2pipdt (dithione) and dcbdt (dithiolato). 1 shows a moderately strong absorption peak in the visible region, which can be related to a HOMO–LUMO transition, where the dcbdt ligand (dithiolato) contributes mostly to the HOMO, and the Bz2pipdt one (dithione) mostly to the LUMO. Thus this transition has ligand-to-ligand charge transfer (CT) character with some contribution of the metal and undergoes negative solvatochromism and molecular quadratic optical nonlinearity (μβ0 = −1296 ×10−48 esu), which was determined by the EFISH (electric-field-induced second-harmonic generation) technique and compared with the values of similar complexes on varying the dithiolato ligand (mnt = maleonitriledithiolato, dmit = 2-thioxo-1,3-dithiole-4,5-dithiolato). Theoretical calculations help to elucidate the role of the dithiolato ligands in affecting the molecular quadratic optical nonlinearity of these complexes.