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

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

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(Cu PS 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,Cu PS 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对相似的氧化还原电位(Eoxd=-0.8 V,Ered=-1.2 V)。具有乙氧取代基的铜配合物CuPSD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。

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 pair of similar redox potentials （Eoxd=-0.8 V, Ered=-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.