Laboratoire de Chimie Organique, Service de Chimie et PhysicoChimie Organiques, Université libre de Bruxelles (ULB), Avenue F.D. Roosevelt 50, CP160/06, 1050, Brussels, Belgium.
Laboratoire de Chimie Organique et Photochimie, Service de Chimie et PhysicoChimie Organiques, Université libre de Bruxelles (ULB), Avenue F.D. Roosevelt 50, CP160/08, 1050, Brussels, Belgium.
Chemistry. 2023 Jul 14;29(40):e202300758. doi: 10.1002/chem.202300758. Epub 2023 May 26.
A new family of heteroleptic diimine-diphosphine copper(I) complexes is reported, with six new complexes compared to benchmark [Cu(bcp)(DPEPhos)]PF . These new complexes are based on 1,4,5,8-tetraazaphenanthrene (TAP) ligands with representative electronic properties as well as substitution patterns and DPEPhos and XantPhos as diphosphine ligands. Their photophysical and electrochemical properties were investigated and correlated with the number and position of substituents on the TAP ligands. Stern-Volmer studies using Hünig's base as reductive quencher demonstrated the influence of the complex photoreduction potential and of the excited state lifetime on the photoreactivity. This study refines the structure-property relationship profile for heteroleptic copper(I) complexes and confirms that such profiles are of high interest to design new copper complexes as optimized photoredox catalysts.
报告了一类新型的异双核二亚胺-二膦铜（I）配合物，与基准 [Cu(bcp)(DPEPhos)]PF 相比，有六个新配合物。这些新配合物基于具有代表性的电子性质以及取代模式和 DPEPhos 和 XantPhos 作为双膦配体的 1,4,5,8-四氮杂菲（TAP）配体。研究了它们的光物理和电化学性质，并与 TAP 配体上取代基的数量和位置相关联。使用 Hünig 碱作为还原猝灭剂的 Stern-Volmer 研究表明，配合物光还原电位和激发态寿命对光反应性有影响。这项研究完善了异双核铜（I）配合物的结构-性质关系概况，并证实此类概况对于设计新的铜配合物作为优化的光氧化还原催化剂具有很高的兴趣。
