Photocatalytic CO2 Reduction Using Various Heteroleptic Diimine-Diphosphine Cu(I) Complexes as Photosensitizers
Photocatalytic CO2 Reduction Using Various Heteroleptic Diimine-Diphosphine Cu(I) Complexes as Photosensitizers
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DOI：
10.3389/fchem.2019.00288
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发表时间：
2019-04-30
影响因子：
5.5
通讯作者：
Tsubomura, Taro
中科院分区：
文献类型：
--
作者：
Yamazaki, Yasuomi;Onoda, Takayuki;Tsubomura, Taro
基于地球上丰富的金属离子的高效氧化还原光敏剂的开发作为贵金属和/或稀有金属光敏剂的替代品是非常可取的。近年来，异电性二亚胺-二膦铜(I)配合物因其作为高效光敏剂的巨大潜力而被广泛研究。本研究利用含有2,9-二甲基-4,7-二苯基-1,10-菲罗啉（dmpp）的一系列铜(I)配合物和各种二膦配体，研究了二膦配体结构对光敏反应能力的影响，以探索适合光敏反应的结构。系统地将二膦配体中两个磷原子之间的亚甲基链数由2个变为4个，并以Cu(I)配合物作为光敏剂进行光催化CO2还原，研究了碳链长度与光敏性的关系。随着碳链长度的增加，CO2还原的周转频率急剧增加。本文的系统研究表明，大的P-Cu-P角可能是提高光敏能力的重要因素之一。
The development of efficient redox-photosensitizers based on the earth-abundant metal ions as an alternative toward noble- and/or rare-metal based photosensitizers is very desirable. In recent years, heteroleptic diimine-diphosphine Cu(I) complexes have been well investigated as one of the most remarkable candidates because of their great potentials as efficient photosensitizers. Here, we investigated the effects of the structure of the diphosphine ligands on the photosensitizing abilities using a series of Cu(I) complexes bearing 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (dmpp) and various diphosphine ligands in order to explore the suitable structure for the photosensitizing reactions. The number of methylene chains between the two phosphorous atoms in the diphosphine ligands was systematically changed from two to four, and the relationship between the length of the carbon chains and the photosensitizing abilities were investigated by conducting photocatalytic CO2 reduction with the Cu(I) complexes as photosensitizers. Turnover frequencies of the CO2 reduction drastically increased with increasing the length of the carbon chains. The systematic study herein reported suggests that the large P-Cu-P angles should be one of the most important factors for enhancing the photosensitizing abilities.