苯甲酸类配体的Co(Ⅱ)配合物合成、晶体结构及光电性能对比

Synthesis,Structure and Comparison of Photo-electric Properties of Co(Ⅱ) Complexes with Benzoic Derivatives Ligand

采用水热和溶剂热方法合成了4种Co（Ⅱ）配合物：[Co（btec）0.5（pz）2]n （1）,[Co（btec）0.5（pz）3]n （2）,[Co（phen）（Hbtc）（H3btc）（H2O）2]·3H2O （3）和[Co（Imh）2（anis）2（H2O）] （4）（H4btec=1,2,4,5-均苯四甲酸,pz=吡唑;H3btc=1,3,5-均苯三甲酸;phen=1,10-邻菲啰啉;Imh=咪唑;Hanis=对甲氧基苯甲酸）。通过X-射线单晶衍射、元素分析、红外光谱（IR）、紫外-可见-近红外（UV-Vis-NIR）漫反射光谱和表面光电压光谱（SPS）对配合物进行了表征。结构分析表明,配合物1是具有2D结构的Co（Ⅱ）配聚物,Co（Ⅱ）为四配位。配合物2～4中,Co（Ⅱ）均为六配位。配合物2为1D链状结构,分子间通过氢键进一步网联成2D。配合物3和4为分子型配合物,然后再分别由氢键进一步网联成3D和2D。SPS结果显示,4种配合物在300～600 nm范围内都呈现正的光伏响应（SPV）,表明它们都具有一定的光-电转换能力。重点是采用SPS技术讨论了配合物结构、空间维度和中心离子配位环境对配合物光电性能的影响,并尝试采用半导体能带理论与配合物的晶体场理论相结合来分析、指认SPS各响应带。

Four Co（Ⅱ） complexes [Co（btec）0.5（pz）2]n （1）, [Co（btec）0.5（pz）3]n （2）, [Co（phen）（Hbtc）（H3btc） （H2O）2]·3H2O （3）, [Co（Imh）2（anis）2（H2O）] （4）, （H4btec=1,2,4,5-benzenetetracarboxylic acid, pz=pyrazole, H3btc=1,3,5-benzene-tricarboxylic acid, phen=1,10-phenanthroline, Imh=imidazole, Hanis=p-anisic acid） were synthesized by hydrothermal method. They were characterized by X-ray single crystal diffraction, IR, elemental analysis, UV-Vis-NIR diffuse reflection spectrum and surface photovoltage spectroscopy （SPS）. The structural analyses indicate that 1 is a Co（Ⅱ） polymer with 2D structure. The Co（Ⅱ） ion is four-coordinate in 1; the ones in 2～4 are both six-coordinate. 2 possesses 1D structure, connected by hydrogen bonds into 2D layer. 3 and 4 are molecular complexes, which are networked into 3D and 2D structures by hydrogen bonds, respectively. Four complexes all exhibit obvious surface photovoltage responses within 300～600 nm in SPS, which indicates that they possess certain photo-electric conversion properties. The influences of structure, dimension of complex and coordination micro-environment of center metal ion on the SPS were discussed emphatically. The energy band theory of semiconductor and crystal field theory are combined to analyze and assign SPS response bands. CCDC： 883535, 1; 883536, 2; 883537, 3; 883538, 4.