Synthesis, Structure, Conductivity, and Calculated Nonlinear Optical Properties of Two Novel Bis(triphenylphosphane)copper(I) Dithiocarbamates

A centrosymmetric binuclear [{Cu(PPh 3 ) 2 } 2 (piperzdtc)] ( 1 ) [piperzdtc 2– = piperazinebis(dithiocarbamate)] and another mononuclear [{Cu(PPh 3 ) 2 }(BzMedtc)] ( 2 ) (BzMedtc – = N ‐benzyl‐ N ‐methyldithiocarbamate) complex have been synthesized and characterized by elemental analyses, IR, 1 H, 13 C, and 31 P NMR spectroscopy and by X‐ray crystallography. The nonlinear optical properties of 2 have been investigated by density functional theory and its electronic absorption bands have been assigned by time‐dependent density functional theory (TD‐DFT). Both complexes are weakly conducting ( σ rt ≈ 10 –8 S cm –1 ) because of the absence of M ··· S/S ··· S intermolecular stacking and exhibit semiconductivity with band gaps of 0.94 and 1.24 eV, respectively.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)