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化学学报
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化学学报 ›› 1999, Vol. 57 ›› Issue (2): 202-209. 上一篇    下一篇

研究论文

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

吴杰颖;田玉鹏;谢复新;倪诗圣;张银汉;段春迎   

  1. 安徽大学化学系.合肥(230090);中国科学技术大学应用化学系.合肥(230026)
  • 发布日期:1999-02-15

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

Wu Jieying;Tian Yupeng;Xie Fuxin;Ni Shisheng;Zhang Yinhan;Duan Chunying   

  1. Anhui Univ, Dept Chem.Hefei(230090);Univ Sci & Technol China, Dept Appl Chem.Hefei(230026);Nanjing Univ, Coordinat Chem State Key Lab. Nanjing(210008)
  • Published:1999-02-15

PDF

474

被引次数

9

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。

关键词: 硫代甲酸P, 阱基, 络合物晶体结构, 非线性光学晶体, 镍络合物, 铜络合物, 钯络合物, 铂络合物

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.

Key words: METHANETHIOIC ACID P, CRYSTAL STRUCTURE OF COMPLEX, NON LINEAR OPTIC CRYSTAL, NICKEL COMPLEX, COPPER COMPLEX, PALLADIUM COMPLEX, PLATINUM COMPLEX

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