浙江大学张兴宏团队报道了磷化氢封端效应实现非共轭聚酯的全色簇发光。相关研究成果于2024年4月8日发表于国际一流学术期刊《美国化学会杂志》。

全色发光体在材料和工程中有着广泛的应用，但基于空间相互作用从非共轭聚合物中构建颜色可调的团簇发光（CL），仍然是一个巨大的挑战。

该文中，研究人员基于磷化氢引发的环氧化物和环状酸酐的共聚，特别是P1-0.5TPP，开发了具有蓝色到红色CL（400–700 nm）的磷化氢封端的非共轭聚酯，其具有红色CL（610 nm），具有32%的高量子产率。

实验和理论计算表明，聚酯中的磷化氢封端效应通过空间（n，π*）相互作用引起构象变化，并诱导磷化氢-酯聚醚。此外，CL的颜色和效率可以很容易地根据磷化氢的类型、聚酯的组成和结构以及浓度来定制。

值得注意的是，研究揭示了聚合物运动（基团、节段和链运动）对源自聚酯内部微观区域的CL的作用。此外，磷化氢封端的非共轭聚酯被证明是非共轭染料和荧光纤维，并且也用于包括白光的多色发光二极管。

该项工作不仅提供了一种基于端基效应的工程策略来制备全色簇状发光体，而且拓宽了材料应用的前景。

附：英文原文

Title: Phosphine-Capped Effects Enable Full-Color Clusteroluminescence in Nonconjugated Polyesters

Author: Bo Chu, Xiong Liu, Xiang Li, Ziteng Zhang, Jing Zhi Sun, Qing Yang, Bin Liu, Haoke Zhang, Chengjian Zhang, Xing-Hong Zhang

Issue&Volume: April 8, 2024

Abstract: Full-color luminophores have advanced applications in materials and engineering, but constructing color-tunable clusteroluminescence (CL) from nonconjugated polymers based on through-space interactions remains a huge challenge. Herein, we develop phosphine-capped nonconjugated polyesters exhibiting blue-to-red CL (400–700 nm) based on phosphine-initiated copolymerization of epoxides and cyclic anhydrides, especially P1-0.5TPP, which exhibits red CL (610 nm) with a high quantum yield of 32%. Experiments and theoretical calculations disclose that the phosphine-capped effect in polyesters brings about conformational changes and induces phosphine–ester clusters by through-space (n,π*) interactions. Moreover, CL colors and efficiencies can be easily tailored by types of phosphines, compositions and structures of polyesters, and concentration. Significantly, the role of polymer motions (group, segmental, and chain motions) on CL originating from microregions inside polyesters is revealed. Further, phosphine-capped nonconjugated polyesters are demonstrated to be nonconjugated dyes and fluorescent fibers and are also used for multicolor light-emitting diodes including white light. This work not only provides an engineering strategy based on the end-group effect to prepare full-color clusteroluminogens but also broadens the prospects for material applications.

DOI: 10.1021/jacs.4c01568

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c01568