烷氧基菲咯啉设计合成及其氮磷杂配铜光敏剂的光解水制氢性能

以功能化氮配体为导向，以4，7-二苯基-1，10-菲咯啉为原料，经季铵化、氧化、卤化和醚化合成了一类新型的2，9-二烷氧基-4，7-二苯基-1，10-菲咯啉配体5a~5e。再以Xantphos为膦配体，通过原位配位方法合成一系列氮磷杂配铜光敏剂（CuPS A~H），在均相光解水制氢体系中研究其光敏活性。制氢结果表明，以2，9-二乙氧基为较佳取代基，CuPS D的催化产氢总转换数（TON）可达270。在光电物理性能分析中，发现这类杂配铜配合物都有一个相似的氧化还原电位（E^oxd=-0.8 V，E^red=-1.2 V）。具有乙氧取代基的铜配合物CuPS D相对于其他取代基的铜基配合物，荧光最弱，表明乙氧基有助于提高荧光淬灭效率，增强铜光敏剂的光化学转换能力。

Alkoxy Phenanthrolines: Design, Synthesis and Heteroleptic Copper Complexes as Photosensitizers in Water Reduction for Hydrogen Production

Aimed in the development of functionalized nitrogen ligands, a series of novel 2,9-dialkoxyl-4,7-diphenyl-1,10-phenanthroline ligands 5a~5e were designed and synthesized from 4,7-diphenyl-1,10-phenanthroline under quaternization, oxidation, halogenation and etherification. Then using Xantphos as phosphorus ligands, a series of heteroleptic copper photosensitizers (CuPS A~H) were obtained by the in-situ method. In homogeneous photocatalytic water reduction system, their photosensitive activity for hydrogen production was studied. Research results show that 2,9-diethoxy is the preferred substituent and the turnover number for hydrogen production (TON) of CuPS D is up to 270. In the analysis of photoelectric physical properties, it is found that this kind of heteroleptic copper complexes have a similar redox potential (E^oxd=-0.8 V, E^red=-1.2 V). Compared with other substituents in Cu-based complexes, CuPS D shows the weakest fluorescence, which indicates the ethoxy substituent could improve the photochemical conversion ability of CuPS by increasing the fluorescence quenching efficiency.