Zhou Zixuan, Chen Xiang, Wang Yang, Hu Chenxi, Li Ting, Wang Shibo, Dong Weifu, Qiao Jinliang
The Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, 1800 Lihu Road, Wuxi 214122, China.
SINOPEC, Beijing Research Institute of Chemical Industry, Beijing 100013, China.
ACS Macro Lett. 2023 Nov 21;12(11):1523-1529. doi: 10.1021/acsmacrolett.3c00549. Epub 2023 Oct 27.
A novel type of fluorescence without large conjugated structures called clusteroluminescence (CL) has attracted a great deal of attention in recent years. Despite its many advantages, the emerging CL still encounters difficulties of low quantum yield (QY) and preliminary mechanisms. In this work, the branched structure was introduced into poly(maleic anhydride--vinyl acetate) by chain transfer monomer. The emission wavelength of the branched copolymers is red-shifted with the increase of branching degree, and the absolute QY of solids can reach up to 29.87%. Further characterizations reveal that the branched structure can improve the flexibility of polymer chains, thereby promoting the intrachain interactions of subgroups. Furthermore, in the case of branched anhydride copolymers, the equilibrium between intrachain interactions and nonradiative transitions holds a crucial significance in determining the QY. This endeavor not only offers new insights into the mechanism of CL but also presents a novel approach to surmount the low QY of anhydride copolymers, thus broadening the horizons of CLgens to unexplored domains.
一种新型的无大共轭结构的荧光，称为簇发光（CL），近年来引起了广泛关注。尽管有许多优点，但新兴的CL仍然面临量子产率（QY）低和初步机制方面的困难。在这项工作中，通过链转移单体将支化结构引入聚（马来酸酐-醋酸乙烯酯）中。支化共聚物的发射波长随着支化度的增加而红移，固体的绝对QY可达29.87%。进一步的表征表明，支化结构可以提高聚合物链的柔韧性，从而促进亚基团的链内相互作用。此外，在支化酸酐共聚物的情况下，链内相互作用和非辐射跃迁之间的平衡在决定QY方面具有至关重要的意义。这项工作不仅为CL的机制提供了新的见解，而且还提出了一种克服酸酐共聚物低QY的新方法，从而将CLgens的视野扩展到未探索的领域。
