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化学学报
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化学学报 ›› 2001, Vol. 59 ›› Issue (9): 1435-1441. 上一篇    下一篇

研究论文

蝴蝶形原子簇化合物[MoOS3Cu2(PyPPh2)3]的制备、晶体结构 和非线性光学性质 研究

牛云垠;郑和根;蔡亚;忻新泉;宋瑛林   

  1. 南京大学配位化学国家重点实验室.南京(210008);哈尔浜工业大学应用物理系
  • 发布日期:2001-09-15

Synthesis, crystal structure and nonlinear optical properties of butterfly-shaped cluster MoOS3Cu2(PyPPh2)3]

Niu Yunyin;Zheng Hegen;Cai Ya;Xin Xinquan;Song Yinglin   

  1. Nanjing Univ, Coordinat Chem State Key Lab.Nanjing(210008)
  • Published:2001-09-15

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采用固相反应方法以[NH4]2[MoS2O2],CuI.Et4NBr和2-)二苯基膦)吡啶(PyPPh2)为原料制备了标题化合物。其结构用单晶分析法测定。测得化合物的分子式为MoOS3Cu2(PyPPh2)3],该晶体结构属三斜晶系，空间群为P1,所得晶胞参数为a=1.16736(4)nm,b=1.42254(5)nm,c=1.68034(6)nm,α=100.07°,β=103.2450(10)°,γ=105.0650(10)°,V=2.53991(15)nm^3,Z=2,Dc=1.504g·cm^-3,F(000)=1166,μ=13.57cm^-1.偏差因子R1=0.0590,wR2=0.1238。簇合物具有高度弯曲的蝴蝶状核，其中MoOS3^2-基团以三齿配体的形式与两个具有不同构型的Cu原子配位，氧原子不参加配位仅以端基形式存在。通过标题化合物在DMF中非线性光学性质的测定，表明其具有较好的非线性吸收和与以往不同的自散焦效应，算得其非线性吸收系数α2=4.4×10^-11m·W^-1，非线性折射系数n2=—8.225×10^-18m^2·W^-1；从而说明外围配体对非线性光学性质也具有大的影响作用。

关键词: 原子簇, 吡啶P, 钼络合物, 铜络合物, 晶体结构, 非线性光学, 簇合物, 光学性质

Solid state reaction of [NH4]2[MoS2O2], CuI and Et4NBr with 2-) diphenylphosphino) pyridine (PyPPh2) results in trinuclear cluster MoOS3Cu2(PyPPh2)3]. Its crystal structure has been determined on a Simens Smart 1-K CCD area-detector diffractometer. The crystal is triclinic, space group P1 with a=1.16736(4)nm, b=1.42254(5)nm, c=1. 68034(6)nm, α=100.07°, β=103.2450(10)°, γ=105.0650(10)°, V=2. 53991(15) nm^3, Z=2 , Dc=1.504g·cm^-3, F(000)=1166, μ=13.57cm^-1. The final R1=0.0590, wR2=0.1238. The cluster is highly bent with a butterfly-shaped core in which the MoOS3^2- unit acts as a tridentate ligand to coordinate with two Cu atoms of different configurations and the O atom serves as a terminal group. Investigation of third- order optical nonlinearity shows that it exhibits considerable nonlinear absorptive and self-defocusing effect with α2=4.4×10^-11m ·W^-1 and n2=-8.225×10^-18m^2·W^-1,respectively. The peripheral ligands also play an important role in the NLO properties of clusters.

Key words: PYRIDINE P, MOLYBDENUM COMPLEX, COPPER COMPLEX, CRYSTAL STRUCTURE, NON LINEAR OPTICS, OPTICAL PROPERTIES

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