肼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

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CuL2^1的晶体结构。晶体属P1空间群,a=0.7835(2),b=1.0530(2),c=1.1816(2)nm,α=100.61(3),β=92.38(3),γ=110.00(3)ⅲ,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。

Synthesis, crystal structure, spectroscopic and third-order nonlinear optical property studies on some dithiocarbazate complexes

Three SN Schiff base ligands derived from dithiocarbazate were prepared. Their neutral bisligand chelates, ML2^1^～^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.