The nickel(Ⅱ) complex with the new ligand of S-benzyl-b-N-[10-ethyl- phenothiazine-3-methylene]dithiocarbazate(HL) crystallizes in the triclinic system, space group P?with a = 7.516(1), b = 11.322(1), c = 13.366(1) ,...The nickel(Ⅱ) complex with the new ligand of S-benzyl-b-N-[10-ethyl- phenothiazine-3-methylene]dithiocarbazate(HL) crystallizes in the triclinic system, space group P?with a = 7.516(1), b = 11.322(1), c = 13.366(1) , a = 84.818(1), b = 81.688(1), g = 76.037(1), V = 1090.26(3) 3, Z = 1, Dc = 1.413 g/cm3, F(000) = 482, m(MoKa) = 0.774 mm-1 (l = 0.7103 ?, R = 0.0573 and wR = 0.1375 for 3357 observed reflections with I ≥ 2s(I). The HL has lost a proton from its tautomeric thiol form and acts as a single negatively charged bidentate ligand coordinating to the nickel ion via the mercapto sulfur and b-nitrogen atoms. The geometry around Ni(Ⅱ) is almost square-planar with two equivalent NiN and NiS bonds. The nonlinear absorption of HL and NiL2 solutions (in DMF) was measured by open-aperture Z-scan technique at the wavelength of 532 nm.展开更多
Two new chiral Schiff base acacen-derivative nickel（II） and copper（II） complexes have been prepared and characterized with IR, electronic, and CD spectra and X-ray crystallography. So-called artifact peaks of soli...Two new chiral Schiff base acacen-derivative nickel（II） and copper（II） complexes have been prepared and characterized with IR, electronic, and CD spectra and X-ray crystallography. So-called artifact peaks of solid-state CD spectra due to restricted to rotate freely of molecules appeared at about 334 and 460 nm for nickel（II） and copper（II） complexes. Changes of intensity of the peaks have been investigated in different matrices such as solid-state （microcrystals or KBr pellets）, PMMA cast films and acetone solutions of various concentrations and pure acetone solutions. Although restricted orientation of molecules in rigid matrices leads to increase the peak intensity toward negative and positive optical rotation for nickel（II） and copper（II） complexes, respectively, the degree of increasing intensity depends on not concentration but viscosity of polymer solutions. Therefore, the artifact CD peaks of solid-state can act as an indicator of environmental viscosity of soft mater matrices.展开更多
基金Supported by a grant for the State Key Program of China (G1998061402) the National Natural Science Foundation of China (29871001, 20071001, and 50272001)
文摘The nickel(Ⅱ) complex with the new ligand of S-benzyl-b-N-[10-ethyl- phenothiazine-3-methylene]dithiocarbazate(HL) crystallizes in the triclinic system, space group P?with a = 7.516(1), b = 11.322(1), c = 13.366(1) , a = 84.818(1), b = 81.688(1), g = 76.037(1), V = 1090.26(3) 3, Z = 1, Dc = 1.413 g/cm3, F(000) = 482, m(MoKa) = 0.774 mm-1 (l = 0.7103 ?, R = 0.0573 and wR = 0.1375 for 3357 observed reflections with I ≥ 2s(I). The HL has lost a proton from its tautomeric thiol form and acts as a single negatively charged bidentate ligand coordinating to the nickel ion via the mercapto sulfur and b-nitrogen atoms. The geometry around Ni(Ⅱ) is almost square-planar with two equivalent NiN and NiS bonds. The nonlinear absorption of HL and NiL2 solutions (in DMF) was measured by open-aperture Z-scan technique at the wavelength of 532 nm.
文摘Two new chiral Schiff base acacen-derivative nickel（II） and copper（II） complexes have been prepared and characterized with IR, electronic, and CD spectra and X-ray crystallography. So-called artifact peaks of solid-state CD spectra due to restricted to rotate freely of molecules appeared at about 334 and 460 nm for nickel（II） and copper（II） complexes. Changes of intensity of the peaks have been investigated in different matrices such as solid-state （microcrystals or KBr pellets）, PMMA cast films and acetone solutions of various concentrations and pure acetone solutions. Although restricted orientation of molecules in rigid matrices leads to increase the peak intensity toward negative and positive optical rotation for nickel（II） and copper（II） complexes, respectively, the degree of increasing intensity depends on not concentration but viscosity of polymer solutions. Therefore, the artifact CD peaks of solid-state can act as an indicator of environmental viscosity of soft mater matrices.
