title: Syntheses, crystal and molecular structures, and properties of some new phenylmercury(II) dithiolate complexes.
abstract: 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.
authors.affiliation: Department of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi, 221005, India. nsingh@bhu.ac.in
authors.forename: Nanhai
authors.initials: N
authors.lastname: Singh
authors.forename: Abhinav
authors.initials: A
authors.lastname: Kumar
authors.forename: Kieran C
authors.initials: KC
authors.lastname: Molloy
authors.forename: Mary F
authors.initials: MF
authors.lastname: Mahon
mesh_terms: D003198:Computer Simulation; D018360:Crystallography, X-Ray; D004553:Electric Conductivity; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D010663:Phenylmercury Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D011789:Quantum Theory; D021241:Spectrometry, Mass, Electrospray Ionization; D013055:Spectrophotometry, Infrared; D013438:Sulfhydryl Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D013696:Temperature
chemical_list: D010663:Phenylmercury Compounds; D013438:Sulfhydryl Compounds