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新型苯并[ ]喹喔啉基杂环铜(I)配合物的强吸收可达 700nm,可用于光收集应用。

Reaching strong absorption up to 700 nm with new benzo[]quinoxaline-based heteroleptic copper(I) complexes for light-harvesting applications.

机构信息

Institute of Organic Chemistry (IOC), Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76137 Karlsruhe, Germany.

Institute of Physical Chemistry-Theoretical Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 2, 76131 Karlsruhe, Germany.

出版信息

Dalton Trans. 2023 Jun 13;52(23):7809-7818. doi: 10.1039/d3dt00902e.

Abstract

Heteroleptic copper(I) complexes, with a diimine as a chromophoric unit and a bulky diphosphine as an ancillary ligand, have the advantage of a reduced pseudo Jahn-Teller effect in their excited state over the corresponding homoleptic bis(diimine) complexes. Nevertheless, their lowest absorption lies generally between 350 to 500 nm. Aiming at a strong absorption in the visible by stable heteroleptic Cu(I) complexes, we designed a novel diimine based on 4-(benzo[]quinoxal-2'-yl)-1,2,3-triazole derivatives. The large π-conjugation of the benzoquinoxaline moiety shifted bathochromically the absorption with regard to other diimine-based Cu(I) complexes. Adding another Cu(I) core broadened the absorption and extended it to considerably longer wavelengths. Moreover, by fine-tuning the structure of the dichelating ligand, we achieved a panchromatic absorption up to 700 nm with a high molar extinction coefficient of 8000 M cm at maximum ( = 570 nm), making this compound attractive for light-harvesting antennae.

摘要

杂化铜(I)配合物,以二亚胺作为发色团单元和大位阻双膦作为辅助配体,与相应的同核双(二亚胺)配合物相比,在激发态下具有降低的伪 Jahn-Teller 效应。然而,它们的最低吸收通常介于 350 到 500nm 之间。为了使稳定的杂化铜(I)配合物在可见光区有强吸收,我们设计了一种基于 4-(苯并[]喹喔啉-2'-基)-1,2,3-三唑衍生物的新型二亚胺。苯并喹喔啉部分的大π共轭使吸收相对于其他基于二亚胺的铜(I)配合物发生红移。添加另一个铜(I)核拓宽了吸收并将其延伸至更长的波长。此外,通过精细调整双螯合配体的结构,我们实现了高达 700nm 的全色吸收,在最大摩尔消光系数为 8000M cm(= 570nm)时,使该化合物成为有吸引力的光收集天线。

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