浙江大学黄飞鹤团队报道了基质响应柱[5]芳烃基有机室温磷光。相关研究成果发表在2023年5月8日出版的国际知名学术期刊《美国化学会杂志》。

室温磷光（RTP）是一种光物理现象，通常与可以用肉眼检测到的长寿命发光有关。一些天然蛋白质显示RTP，某些人造聚合物也是如此。在这两种情况下，RTP都归因于通过空间电子通信的有效分子内通信。然而，能够实现RTP的内部电子通信的小分子相对较少。

该文中，研究人员描述了一种烷基卤化物响应RTP系统，该系统由间甲酰基苯基柱[5]芳烃衍生物组成，该衍生物支持柱芳烃腔内的有效空间电荷转移（TSCT）。用溴乙烷（柱[5]芳烃主体的一种含重原子的客体）处理有助于提高排放。含对甲酰基苯基的柱[5]芳烃体系在产生RTP效应方面被证明是无效的。基于单晶X射线衍射分析的量子化学计算，研究人员深入了解了控制柱[5]芳烃的1,4-二甲氧基苯供体单元和甲酰基苯基之间的TSCT的结构决定因素，以及相关的能隙和系统间交叉通道。研究认为，目前的系统和相关的机理分析为设计具有可调RTP特征的新型小分子提供了基础。

附：英文原文

Title: Substrate-Responsive Pillar[5]arene-Based Organic Room-Temperature Phosphorescence

Author: Huangtianzhi Zhu, Junkai Liu, Yitao Wu, Lei Wang, Haoke Zhang, Qi Li, Hu Wang, Hao Xing, Jonathan L. Sessler, Feihe Huang

Issue&Volume: May 8, 2023

Abstract: Room-temperature phosphorescence (RTP) is a photophysical phenomenon typically associated with a long-lived emission that can be detected by the unaided eye. Several natural proteins display RTP, as do certain artificial polymers. In both cases, the RTP is ascribed to effective intramolecular through-space electronic communication. However, small molecules with internal electronic communication that enable RTP are relatively rare. Herein, we describe an alkyl halide-responsive RTP system consisting of a meta-formylphenyl-bearing pillar[5]arene derivative that supports effective through-space charge transfer (TSCT) within the pillararene cavity. Treatment with bromoethane, a heavy atom-containing guest for the pillar[5]arene host, serves to enhance the emission. An isomeric para-formylphenyl-bearing pillar[5]arene system proved ineffective in producing an RTP effect. Quantum chemical calculations based on single-crystal X-ray diffraction analyses provided insights into the structural determinants governing TSCT between the 1,4-dimethoxybenzene donor units and the formylphenyl groups of the pillar[5]arene, as well as the associated energy gaps and intersystem crossing channels. We believe that the present system and the associated mechanistic analysis provide the foundation for design of new small molecule with tunable RTP features.

DOI: 10.1021/jacs.3c00711

Source: https://pubs.acs.org/doi/10.1021/jacs.3c00711