Syntheses, crystal and molecular structures, and properties of some new phenylmercury(II) dithiolate complexes.

A series of new phenylmercury(II) dithio complexes [PhHg(Bun2dtc)] (; Bun2dtc-=di-n-butyldithiocarbamate), [PhHg(morphdtc)] (; morphdtc-=morpholinedithiocarbamate), [PhHg(Bz2dtc)] (; Bz2dtc-=dibenzyldithiocarbamate), [PhHg(methoxethxant)] (; methoxethxant-=2-methoxyethylxanthate) [(PhHg)2NED] (; NED2-=1-nitroethylene-2,2-dithiolate) and [(PhHg)2CDC] (; CDC2-=cyanodithioimidocarbonate) have been prepared and characterized by elemental analysis, UV-Vis, IR, 1H and 13C NMR spectra and mass spectrometry. The crystal structures of , and showed a linear Hg(II) core at the center of the molecules. The weak intra- and intermolecular HgS interactions provide a molecular chain framework. The reaction of PhHgO2CCH3 with Bun2dtcH gave the known dimeric complex Hg(Bun2dtc)2 while the Ni(O2CCH3)2 mediated reaction gave instead of the expected heterobimetallic complex [PhHgNi(Bun2CS2)2]O2CCH3 which has been corroborated by natural charges at each atom obtained at the density functional level (DFT) of theory. Upon excitation at 358 nm exhibited a medium strong photoluminescence emission at 420 nm as a consequence of intraligand pi-->pi* transitions. The electronic absorption bands of were assigned from time dependent density functional theory (TD-DFT) calculations. Geometrical configurations of , and have been optimized using the DFT method. All of the complexes are weakly conducting (sigmart approximately 10(-12) S cm(-1)). However and exhibited semiconductivity with band gaps of 0.39 and 0.94 eV respectively.