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手性卡宾-铜(I)-酰胺对映体的聚集依赖性圆偏振发光和热激活延迟荧光
作者:小柯机器人 发布时间:2022/9/21 13:37:15

武汉大学龚少龙团队报道了手性卡宾-铜(I)-酰胺对映体的聚集依赖性圆偏振发光和热激活延迟荧光。相关研究成果发表在2022年9月15日出版的《德国应用化学》。

近年来,发光卡宾金属酰胺(CMA)配合物和手性活性材料蓬勃发展,而手性活性CMA配合物迄今尚未报道。

研究人员首次利用手性苯基取代的N-杂环卡宾作为CMA基序中的受体配体,合成了一对手性Cu(I)基CMA对映体,即(R,R)-PSIPr*-Cu DMAC和(S,S)-PSIP R*-Cu-DMAC。基于Cu(I)的CMA对映体表现出聚集诱导的圆极化发光,其发光不对称因子高达+0.027,首次在CMA络合物中报道。这种成功源于晶体中CMA对映体的有限配体-配体旋转自由度和不对称堆积模式(螺旋结构)。此外,这些Cu(I)对映体显示出激发聚集依赖的热激活延迟荧光特性。

研究结果从聚集态的角度为手性CMA配合物的光学性质带来了新的见解。

附:英文原文

Title: Aggregation-Dependent Circularly Polarized Luminescence and Thermally Activated Delayed Fluorescence from Chiral Carbene-Cu(I)-Amide Enantiomers

Author: Ao Ying, Yuhan Ai, Chuluo Yang, Shaolong Gong

Issue&Volume: 2022-09-15

Abstract: Luminescent carbene-metal-amide (CMA) complexes and chiroptical-active materials have been bursting into bloom in recent years, while chiroptical-active CMA complexes has not been reported so far. For the first time, a pair of chiral Cu(I)-based CMA enantiomers,  (R,R)-  PSIPr*-Cu-DMAC  and  (S,S)  -PSIPr*-Cu-DMAC  , were developed by using chiral phenyl-substituted  N  -heterocyclic carbenes as acceptor ligands in the CMA motif. The Cu(I)-based CMA enantiomers exhibited aggregation-induced circularly polarized luminescence with a large luminescence dissymmetry factor of up to +0.027, first reported in CMA complexes. This success originates from the limited ligand-ligand rotation freedom and asymmetrical packing pattern (helical structure) of CMA enantiomers in the crystals. Moreover, these Cu(I) enantiomers displayed inspiring aggregation-dependent thermally activated delayed fluorescence properties. These findings bring new insights into optical properties of chiral CMA complexes from perspective of aggregation states.

DOI: 10.1002/anie.202210490

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202210490

期刊信息

Angewandte Chemie:《德国应用化学》,创刊于1887年。隶属于德国化学会,最新IF:12.959
官方网址:https://onlinelibrary.wiley.com/journal/15213773
投稿链接:https://www.editorialmanager.com/anie/default.aspx