含咪唑基配体的Co(Ⅱ)超分子配合物的合成、晶体结构和光谱性质

采用改进的固相Wittig反应, 合成了一种新型的具有电子给受体和π共轭结构的咪唑衍生物1-{反式4-4-(-N,N-二乙基氨基)苯乙烯基]苯}咪唑(C21H23N3, 简作L). 室温下, 将L与Co(SCN)2在甲醇中反应, 合成了配合物Co(SCN)2(C21H23N3)4. X射线单晶衍射分析结果表明, 该晶体属于三斜晶系, P1空间群, 晶胞参数a=0.931 7(3) nm, b=1.275 3(4) nm, c=1.669 1(5) nm, α= 89.521(5)°, β=84.591(5)°, γ=80.052(5)°, V=1.944 6(11) nm3, Z=1, μ=0.329 mm-1, Dc=1.234 Mg/m3, F(000)=765, R1=0.060 1, wR=0.138 1, GOF=1.030, 中心原子Co(Ⅱ)的配位数为6, 分别与来自4个L的咪唑N及2个SCN-的N配位, 形成八面体的空间构型. 配合物分子通过非典型氢键和π-π堆积作用形成三维超分子结构. 研究结果表明, 配合物具有很好的光学性质.

Synthesis, Crystal Structure and Optical Properties of a Novel Co(Ⅱ) Complex Containing Imidazole Ligand

A novel imidazole derivative with π-conjugated system, 1-trans-4-(4-diethylaminostyryl)phenyl] imidazole(L) and its complex, CoL4(SCN)2, were prepared. The structure of the complex was determined by single crystal X-ray diffraction analysis. The crystal is of orthorhombic system, space group P1 with a=0.931 7(3) nm, b=1.275 3(4) nm, c=1.669 1(5) nm, α=89.521(5)°, β=84.591(5)°, γ=80.052(5)°, V=1.944 6(11) nm3, Z=1, μ=0.329 mm-1, Dc=1.234 Mg/m3, F(000)=765, R1=0.060 1, wR=0.138 1, GOF=1.030. In the molecular structure of Co(SCN)2L4, CoⅡ atom is six coordinated by four N atoms of the ligands(L) and two N atoms of thiocyanate to form an octahedral geometry. The untypical hydrogen bonds and π-π stacking interaction lead to three-dimensional supramolecular formation. The optical properties were experimentally studied.