含哌嗪基元的金属超分子聚合物的合成、光物理和电化学性质

Synthesis,Photophysical and Electrochemical Properties of Metallo-supramolecular Polymers Containing Piperazine Moiety

设计合成了以哌嗪为电子给体,2,2′∶6′,2″-三联吡啶为电子受体的超分子聚合物构筑单元PPTPY,通过Zn2+、Cd2+诱导自组装聚合,得到相应的金属超分子聚合物PPTPY-Zn和PPTPY-Cd,并通过核磁共振对其结构进行了确认。紫外-可见吸收光谱研究表明,在N,N-二甲基乙酰胺(DMAc)溶剂中,其最大吸峰位置相对于聚合前分别红移了74nm和59nm,聚合物PPTPY-Zn和PPTPY-Cd的固态膜荧光发射峰在549nm和552nm,且半峰宽为111nm和113nm,荧光颜色表现为橙光发射。循环伏安性质研究表明,单体和聚合物均表现出明显的氧化峰,PPTPY-Zn和PPTPY-Cd的起始氧化电位分别为0.75V和0.79V,均低于PPTPY的0.84V。

The monomer PPTPY with piperazine as electron donor and 2,2′∶6′,2″-terpyridine as electron acceptor was synthesized.Via Zn2+and Cd2+-directed self-assembly polymerization,the metallo-supramolecular polymers PPTPY-Zn and PPTPY-Cd were obtained.And their structures were determined by NMR.The UV absorption spectra of PPTPY-Zn and PPTPY-Cd showed red shifted 74nm and 59nm respectively in comparison to building block monomer PPTPY in DMAc solution.And the emission maxima of PPTPY-Zn and PPTPY-Cd films are at 549nm and 552nm with half-peak width of 111nm and 113nm,which exhibited orange emission,in films respectively.The cyclic voltammogram showed that the onset oxidative potential of PPTPY-Zn and PPTPY-Cd were 0.75Vand 0.79V,both of that were lower than that of 0.84Vfor PPTPY.