M-均苯三甲酸基配聚物(M=Cu和Co)的合成、结构及光伏性能

Synthesis,Structure and Photovoltaic Property of M-1,3,5-benzenetricarboxylato Coordination Polymers(M=Cu and Co)

采用水热方法合成2种均苯三甲酸根配位聚合物{[Cu2(Hbtc)2(H2O)6]·ppz·H2O}n(1)和{[Co2(btc)2(H2O)6]·(H2ppz)·(H2O)}n(2)(H3btc=均苯三甲酸,ppz=哌嗪),通过红外光谱(IR)、紫外-可见-近红外吸收光谱(UV-Vis-NIR)、元素分析和X射线单晶衍射(XRD)对配位聚合物进行表征,利用表面光电压光谱(SPS)考察配位聚合物的光伏性能,并将SPS与UV-Vis吸收光谱进行关联,采用半导体能带理论与晶体场理论分析且指认各响应带.结果表明:配位聚合物1和2均属于三斜晶系,P-1空间群;二者具有均苯三甲酸根桥连的1D链状结构,不对称单元中均包含2个晶体学不等效的M(Ⅱ)离子(M1=Cu,M2=Co);二者中心金属离子的配位构型不同,相同有机分子的存在形式不同;2种配位聚合物在紫外-可见光诱导下均产生光伏响应,且配位聚合物中心离子的配位环境对光伏响应影响较大.

Two 1,3,5-benzenetricarboxylato coordination polymers {[Cu2（Hbtc）2（H2O）6]·ppz· H2O}n（1）and {[Co2（btc）2（H2O）6]·（H2ppz）·（H2O）}n（2）,（H3btc=1,3,5-benzenetricarboxylic acid,ppz=piperazine）have been hydrothermally synthesized and characterized by IR,UV-Vis-NIR, elemental analysis and X-ray single crystal diffraction. Structural analysis reveals that the two coordination polymers both crystallize in the triclinic system with P-1 space group and both possess the M1-btc-M2-btc-M1-polymeric zigzag-chain structure,but the coordination geometry around metal ions is different and the same organic molecules exhibit different forms.The photovoltaic property was investigated by surface photovoltage spectroscopy （SPS ）. The results reveal that the two polymers all exhibit surface photovoltage responses under UV-Vis light-inducement in SPS,and the coordination environment of the metallic ion affect the response scope.The SPS responses were analyzed and assigned by the combination of the energy band theory of semi-conductor and crystal field＆amp;nbsp;theory.