21439-58-7Relevant articles and documents
Syntheses, crystal and molecular structures, and properties of some new phenylmercury(ii) dithiolate complexes
Singh, Nanhai,Kumar, Abhinav,Molloy, Kieran C.,Mahon, Mary F.
, p. 4999 - 5007 (2009/02/05)
A series of new phenylmercury(ii) dithio complexes [PhHg(Bu n2dtc)] (1; Bun2dtc- = di-n-butyldithiocarbamate), [PhHg(morphdtc)] (2; morphdtc- = morpholinedithiocarbamate), [PhHg(Bz2dtc)] (3; Bz2dtc - = dibenzyldithiocarbamate), [PhHg(methoxethxant)] (4; methoxethxant- = 2-methoxyethylxanthate) [(PhHg)2NED] (5; NED2- = 1-nitroethylene-2,2-dithiolate) and [(PhHg)2CDC] (6; 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 1, 2 and 3 showed a linear Hg(ii) core at the center of the molecules. The weak intra- and intermolecular Hg-S interactions provide a molecular chain framework. The reaction of PhHgO2CCH3 with Bu n2dtcH gave the known dimeric complex Hg(Bu n2dtc)2 while the Ni(O2CCH 3)2 mediated reaction gave 1 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 3 exhibited a medium strong photoluminescence emission at 420 nm as a consequence of intraligand π → π* transitions. The electronic absorption bands of 3 were assigned from time dependent density functional theory (TD-DFT) calculations. Geometrical configurations of 4, 5 and 6 have been optimized using the DFT method. All of the complexes are weakly conducting (σrt ～ 10-12 S cm-1). However 2 and 6 exhibited semiconductivity with band gaps of 0.39 and 0.94 eV respectively. The Royal Society of Chemistry 2008.
