TADF-emitting copper(i) and silver(i) complexes featuring intra-ligand charge transfer based on a donor–acceptor–donor ligand†

IF 2.7 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY
Xinwei Wang, Weijun Li, Xiao Li, Chenlu Hou, Sanyue Wei, Wenxin Lei and Xu-Lin Chen
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Abstract

Copper(I) and silver(I) complexes have garnered significant interest as photoluminescent and electroluminescent emitters. Developing efficiently luminescent copper(I) and silver(I) complexes relies on the rational design of ligands, based on a deep understanding of the relationships between structure, excited states, and photophysical properties. Herein, a copper(I) complex and a silver(I) complex, namely Cu(Ac-phen)XP·BF4 and Ag(Ac-phen)XP·BF4, were synthesized based on a donor–acceptor–donor (D–A–D) type diimine ligand and a bisphosphine ligand. Cu(Ac-phen)XP·BF4 and Ag(Ac-phen)XP·BF4 in the solid state exhibit red and orange-yellow emission with photoluminescent quantum yields of 18% and 40%, and emission lifetimes of 1.2 μs and 7.8 μs, respectively. Theoretical and experimental investigations demonstrate that both complexes emit efficient thermally activated delayed fluorescence (TADF) from excited states dominated by intra-ligand charge transfer (ILCT) transitions. The ILCT emissive states are attributed to the stronger electron-donating ability of the A–D–A type ligand compared to the d10 copper and silver centers. The distinct metal coordination effects of the copper and silver centers lead to different levels of LUMO stabilization in the diimine ligand, resulting in different emissions for the copper(I) and silver(I) complexes.

Abstract Image

tadf -发射铜(i)和银(i)配合物,具有基于供体-受体-供体配体†的配体内电荷转移
铜(I)和银(I)配合物作为光致发光和电致发光的发射体已经引起了人们极大的兴趣。开发高效发光的铜(I)和银(I)配合物依赖于配体的合理设计,基于对结构、激发态和光物理性质之间关系的深刻理解。本文以供体-受体-供体(D-A-D)型二亚胺配体和双膦配体为基础,合成了铜(I)配合物Cu(Ac-phen)XP·BF4和银(I)配合物Ag(Ac-phen)XP·BF4。Cu(Ac-phen)XP·BF4和Ag(Ac-phen)XP·BF4表现出红色和橙黄色的发光特性,光致发光量子产率分别为18%和40%,发光寿命分别为1.2 μs和7.8 μs。理论和实验研究表明,这两种配合物都能从由配体内电荷转移(ILCT)转变主导的激发态发射出高效的热激活延迟荧光(TADF)。与d10铜和银中心相比,A-D-A型配体具有更强的给电子能力,这是ILCT发射态的原因。铜和银中心不同的金属配位效应导致二亚胺配体中LUMO的稳定水平不同,从而导致铜(I)和银(I)配合物的辐射不同。
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来源期刊
New Journal of Chemistry
New Journal of Chemistry 化学-化学综合
CiteScore
5.30
自引率
6.10%
发文量
1832
审稿时长
2 months
期刊介绍: A journal for new directions in chemistry
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