Citation: WU Qing-An, CHEN Hao, HUANG Dao-Chen, XIA Liang-Min, WANG Xiao-Jing, LOU Wen-Ya, WU Xiao-Feng, LUO Shu-Ping. Alkoxy Phenanthrolines: Design, Synthesis and Heteroleptic Copper Complexes as Photosensitizers in Water Reduction for Hydrogen Production[J]. Chinese Journal of Inorganic Chemistry, ;2018, 34(2): 270-276. doi: 10.11862/CJIC.2018.057 shu

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

1.
State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, China
2.
Yiwu Science and Technology Research Institute, Zhejiang University of Technology, Yiwu, Zhejiang 322001, China

Corresponding author: LUO Shu-Ping, Luoshuping@zjut.edu
Received Date: 11 September 2017
Revised Date: 8 November 2017

Figures(6)

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 (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.
- phenanthroline-modification,
- copper photosensitizer,
- hydrogen evolution from water splitting,
- structure-activation relationship
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