大环芳烃菲咯啉的设计、合成及其铜光敏剂光解水制氢性能  

Macrocyclic Arenes Derived Phenanthrolines:Design,Synthesis and Application at Heteroleptic Copper Complexes for Photocatalytic Hydrogen Evolution from Water

作　　者：许萌[1] 俞晓聪 刘雪粉[2] 陈浩[1] 范金轩 王天琦 吴庆安[1] 罗书平[1] XU Meng;YU Xiao‑Cong;LIU Xue‑Fen;CHEN Hao;FAN Jin‑Xuan;WANG Tian‑Qi;WU Qing‑An;LUO Shu‑Ping(State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology,Zhejiang University of Technology,Hangzhou 310014,China;Qianjiang College,Hangzhou Normal University,Hangzhou 310018,China)

机构地区：[1]浙江工业大学绿色化学合成技术国家重点实验室培育基地,杭州310014 [2]杭州师范大学钱江学院,杭州310018

出　　处：《无机化学学报》2021年第9期1597-1605,共9页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21376222);浙江省自然科学基金(No.LY18B060011)资助。

摘　　要：设计、合成了一类4,7位为大环芳烃的菲咯啉二齿氮配体,可与铜.和Xantphos原位配位,获得一系列新型氮磷杂配铜光敏剂CuPS 1~CuPS 6,在均相光解水制氢体系中研究其光敏活性及构效关系。实验结果表明,在菲咯啉4,7位引入芳基有利于提高其光敏活性,1-萘基取代的CuPS 3有最好的制氢活性,光解水制氢转化数(TON)达957。通过理论计算对比分析,1-萘基取代基与菲咯啉母核具有较大的二面角,对铜配合物的激发态有较好的保护作用,因此CuPS 3表现出较高的荧光量子产率(0.036)和较长的激发态寿命(1.36μs)。A series of macrocyclic arenes derived phenanthrolines have been designed and synthesized,which could form a series of novel heteroleptic copper photosensitizersCuPS 1~CuPS 6 with Xantphos as phosphorus ligands.The photosensitive activity ofCuPS 1~CuPS 6 was studied in homogeneous photocatalytic water reduction system for hydrogen production.The research results showed that 1-naphthyl was the preferred substituent and the turnover number(TON)ofCuPS 3 for hydrogen production was up to 957.Through theoretical calculation and com-parative analysis,a larger dihedral angle of the 1-naphthyl substituent and the phenanthroline nucleus has a better steric effect to protect the excited state of the copper complex.Thus,CuPS 3 displayed a higher fluorescence quan-tum yield(0.036)and a longer excited state lifetime(1.36μs).

关 键 词：大环芳烃 菲咯啉 铜光敏剂 光解水 制氢 

分 类 号：O614.121[理学—无机化学]