脱基硫代甲酸酯配合物的合成、晶体结构、光谱及三阶非线性光学性质研究

Synthesis, Crystal Structure, Spectroscopic and Third-Order Nonlinear Optical Property Studies on Some Dithiocarbazate Complexes

报道三种有推拉电子基团的肼基硫代酸酯衍生物配体(HL^(1～3)).此类配体与二价过渡金属离子配位时脱去一质子,形成D-M-D和A-M-A(D=给体,M=金属,A=受体)类型、含有共轭体系的中性配合物.本文集中研究了该类配体的镍、铜、钯、铂配合物的IR、磁化率、ESR谱,电子光谱和三阶非线性光学性质,通过光谱研究初步确定了它们均为平面正方形构型配合物,文中还报道了CuL_2~1晶体结构.晶体属P(?)空间群,a=0.7835(2),b=1.0530(2),c=1.1816(2)nm,a=100.61(3),β=92.38(3),γ=110.00(3)°,Z=1,最终的R因子为0.063.通过晶体结构测试,进一步确定铜配合物的结构为平面构型.

Three SN Schiff base ligands derived from dithiocarbazate were prepared. Their neutral bis-ligand chelates, MI21-3[M = Ni( Ⅱ ), Cu(Ⅱ) ,Pd(Ⅱ) and Pt(Ⅱ)], forming D-M-D and A-M-A type complexes were also prepared and characterized (D = donor, M = metal A = acceptor). Magnetic and spectroscopic data suggest a square-planar structure for the complexes. ESR spectra and variable-temperature magnetic susceptibility data supported a square-planar structure of Cu ( Ⅱ ) chelate too. Single crystal X-ray diffraction analysis of the copper( Ⅱ ) chelate established that the Schiff base ligand lost a proton from its tautomeric thiol form and coordinated to metal via the mercapto sulfur and β-nitrogen. The geometry around Cu( Ⅱ) is square-planar with two equivalent Cu-N and Cu-S bonds, forming an electronic delocalization system. The third-order NLO properties of them were also studied. The results show that the electro-donation group is quite helpful for the complexes exhibit higher third-order response.