The geometric configurations of binuclear Zinc( complex Zn2[(n-Bu)2NCSS]4 and the ligand Na[(n-Bu)2 NCSS] have been optimized by B3LYP quantum chemical method. The electronic structures have been performed by density ...The geometric configurations of binuclear Zinc( complex Zn2[(n-Bu)2NCSS]4 and the ligand Na[(n-Bu)2 NCSS] have been optimized by B3LYP quantum chemical method. The electronic structures have been performed by density functional theory at B3LYP/6-31G* level. The electronic spectrums of the complex and ligand were calculated by ZINDO/S-CIS method. It is indicated from the calculation that: (1) The coordination effect of bridging ligand is bigger than that of chelating one, and the bridging ligands also translate more charge to Zn than the chelating one. (2) The calculated results about electronic spectrums are similarly to experimental measurement, and farther explain that absorption band at λ=267 nm of complex is assigned to two n → π* transitions :one arising from the bridging ligands and the another mainly arising from the chelating ligands;but absorption band at λ=236 nm of complex is assigned to π → π* transition which the electron mainly translates from the bridging ligands to the chelating ligands. (3) By consideration of delocalization and polar effects in coordination, the charge transfer from ligand to metal decreases the π-π and p-π conjugation effects in the chromophore group NCS2 and to increase the energy needed for the π → π* and n → π* transitions, and results in the absorption bands shifting towards the short wavelength direction.展开更多
Di(o-fluorbenzyl)tin bis(dithiotetrahydropyrrolcarbamate) (1) and di(p-chlorbenzyl)tin bis(dithiomethylcarbamate) (2) were synthesized. Their structure were characterized by elementary analysis, IR and 1H NMR and the ...Di(o-fluorbenzyl)tin bis(dithiotetrahydropyrrolcarbamate) (1) and di(p-chlorbenzyl)tin bis(dithiomethylcarbamate) (2) were synthesized. Their structure were characterized by elementary analysis, IR and 1H NMR and the crystal structure were determined by X-ray single crystal diffraction. The crystal of complex 1 belongs to orthorhombic with space group Pccn, a=2.096 1(12) nm, b=1.018 5(6) nm, c=1.205 9(7) nm, Z=4, V=2.574(2) nm3, Dc=1.624 g·cm-3, μ(MoKα)=1.348 mm-1, F(000)=1 272,R1=0.038 7, wR2=0.088 5. The crystal of complex 2 belongs to monoclinic with space group C2/c, a=1.531 3(16), b=1.868 4(19), c=0.951 8(10) nm, β=112.602(14)°, Z=4, V=2.514(5) nm3, Dc=1.612 g·cm-3, μ(MoKα)=1.572 mm-1, R1=0.025 4, wR2=0.070 4. In the complexes 1 and 2, the structures consist of discrete molecules containing six-coordinate tin atom in a distorted octahedron configuration. In crystal of complex 1, molecules are packed in the unit cell in one-dimensional chain structure through a S...S interaction between adjacent molecule. CCDC: 225420, 1; 225421, 2.展开更多
文摘The geometric configurations of binuclear Zinc( complex Zn2[(n-Bu)2NCSS]4 and the ligand Na[(n-Bu)2 NCSS] have been optimized by B3LYP quantum chemical method. The electronic structures have been performed by density functional theory at B3LYP/6-31G* level. The electronic spectrums of the complex and ligand were calculated by ZINDO/S-CIS method. It is indicated from the calculation that: (1) The coordination effect of bridging ligand is bigger than that of chelating one, and the bridging ligands also translate more charge to Zn than the chelating one. (2) The calculated results about electronic spectrums are similarly to experimental measurement, and farther explain that absorption band at λ=267 nm of complex is assigned to two n → π* transitions :one arising from the bridging ligands and the another mainly arising from the chelating ligands;but absorption band at λ=236 nm of complex is assigned to π → π* transition which the electron mainly translates from the bridging ligands to the chelating ligands. (3) By consideration of delocalization and polar effects in coordination, the charge transfer from ligand to metal decreases the π-π and p-π conjugation effects in the chromophore group NCS2 and to increase the energy needed for the π → π* and n → π* transitions, and results in the absorption bands shifting towards the short wavelength direction.
文摘Di(o-fluorbenzyl)tin bis(dithiotetrahydropyrrolcarbamate) (1) and di(p-chlorbenzyl)tin bis(dithiomethylcarbamate) (2) were synthesized. Their structure were characterized by elementary analysis, IR and 1H NMR and the crystal structure were determined by X-ray single crystal diffraction. The crystal of complex 1 belongs to orthorhombic with space group Pccn, a=2.096 1(12) nm, b=1.018 5(6) nm, c=1.205 9(7) nm, Z=4, V=2.574(2) nm3, Dc=1.624 g·cm-3, μ(MoKα)=1.348 mm-1, F(000)=1 272,R1=0.038 7, wR2=0.088 5. The crystal of complex 2 belongs to monoclinic with space group C2/c, a=1.531 3(16), b=1.868 4(19), c=0.951 8(10) nm, β=112.602(14)°, Z=4, V=2.514(5) nm3, Dc=1.612 g·cm-3, μ(MoKα)=1.572 mm-1, R1=0.025 4, wR2=0.070 4. In the complexes 1 and 2, the structures consist of discrete molecules containing six-coordinate tin atom in a distorted octahedron configuration. In crystal of complex 1, molecules are packed in the unit cell in one-dimensional chain structure through a S...S interaction between adjacent molecule. CCDC: 225420, 1; 225421, 2.
