系列Ni(Ⅱ)配位超分子的晶体结构及表面光电压光谱分析

A series of Ni(Ⅱ) coordination supramolecules: crystal structure and analysis of surface photovoltage spectra

采用水热和水浴合成法,以不同的刚性和柔性有机羧酸衍生物为配体,合成了2个Ni(Ⅱ)配合物:[Ni(otpha)(Imh)3(H2O)2].H2O(1)(H2otpha=邻苯二甲酸),[Ni(mal)(phen)(H2O)2](2)(mal=丙二酸,phen=1,10-菲啰啉).采用X-射线单晶衍射确定2个配合物的分子结构.结构分析表明,配合物1和2均属于单斜晶系,空间群分别为P2(1)/n和P2(1)/c,中心金属Ni(Ⅱ)离子均为6配位,并由氢键将其分别连接成具有3D和1D结构的超分子.采用表面光电压光谱(SPS)研究了2个配合物的表面光电性能.结果表明,它们在300～800nm范围内均呈现出正的表面光伏响应,表明它们具有一定的光-电转换能力.对2个配合物的UV-Vis-NIR吸收光谱进行了测定和分析指认,并分别将它们的SPS谱与UV-Vis吸收光谱进行了对比分析,发现SPS谱中响应带的数量和位置与其UV-Vis吸收光谱中的吸收峰呈现出一致性.

Two complexes [Ni（otpha）（Imh）3（H2O）2]·H2O（1）,[Ni（mal）（phen）（H2O）2]（2）have been synthesized by hydrothermal method and bath Synthesis method with the derivatives of different rigid and flexible organic carboxylic acid as ligands.The molecular structures of the two complexes were determined by single crystal X-ray diffraction.Structural analyses show that the two complexes are monoclinic crystal system,P2（1）/n and P2（1）/c space group,the central Ni（Ⅱ）ion are six-coordinated which are linked into 3D and 1D supramolecule by hydrogen bonds,respectively.The photo-electric properties were investigated by surface photovoltage spectroscopy（SPS）.The results indicate that the two complexes exhibit positive surface photovoltage responses in the range of 300 ~ 800 nm,indicating that they all possess certain photo-electric conversion properties.In addition,the UV-Vis-NIR spectra of the two complexes were measured and analyzed,SPS spectra of the two complexes were compared with UV-Vis spectra,the number and position of response bands in SPS spectra is in accord with those of absorption peaks in UV-Vis spectra.