含氟菲咯啉的设计合成及其杂配铜配合物的光解水性能

Fluoric Phenanthrolines and Their Heteroleptic Copper Complexes:Synthesis and Application in Photocatalytic Hydrogen Evolution from Water

设计合成新型含氟菲咯啉二齿配体,与六氟磷酸四乙腈合铜及磷配体Xantphos进行配位,得到相应的铜基配合物(CP1~CP4),再以此配合物作为光敏剂用于光催化水解制氢,发现其在均相光解水体系中表现出较好的光敏活性,制氢总转换数(TON)可达896。结合对所选的配合物进行吸收光谱和荧光发射光谱的测试结果可知,此配合物在溶液中也具有很好的稳定性,不会发生配体的重组现象。荧光淬灭实验表明,氧化淬灭为光解水过程中主要的淬灭途径。此外,对这类配合物作为光敏剂的构效关系及其内在机理进行了初步的解释与探讨。

A series of novel bidentate ligands of fluoro phenanthrolines were designed and synthesized,which could formulate a series of heteroleptic copper photosensitizers CP1~CP4 with Cu(MeCN)4PF6 and Xantphos as P ligand.The photosensitive activities of this copper complex were researched in water reduction system,and the turnover number(TON)of hydrogen evolution was up to 896.The absorption spectrum and fluorescence emission spectrum of the copper complexes indicated the good stability in solution.The oxidation quenching is the main quenching path⁃way in water reduction system,which was confirmed by the fluorescence quenching experiments.Moreover,a pre⁃liminary explanation and discussion of the structure⁃activity relationship and the mechanism of photocatalytic hydro⁃gen evolution from water were carried out.