Li Haomin, Lei Huanyu, Ma Shudeng, Song Tianfu, Li Yan, Yu Haifeng
School of Materials Science and Engineering, Beijing Advanced Innovation Centre for Biomedical Engineering, Beihang University, Beijing, 100191, China.
School of Materials Science and Engineering, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, Peking University, Beijing, 100871, China.
Angew Chem Int Ed Engl. 2024 Jan 2;63(1):e202312185. doi: 10.1002/anie.202312185. Epub 2023 Nov 29.
Photoluminescence is one of the most meticulous ways to manipulate light energy. Typical photoluminescent emitters are mostly stable substances with a pure photophysical process of spontaneous photon-emission from their excited states. Intermediate emitters are elusive attributing to their synchronous energy transfer process including photophysical and incomplete photochemical pathways. An intermediate emitter containing radicals is more difficult to be observed due to its inherent chemical reactivity. Here, these challenges are overcome by spontaneously formed space limitations in polymer crosslinking networks meanwhile chemically active intermediates are captured. These doublet intermediates exhibit unique long-wavelength emissions under chemically crosslinking confinement conditions, and their luminous mechanism provides a novel perspective for designing intermediate emitters with liquid-crystal character and photoresponsive features towards spatiotemporal encryption, promising for the detection of photochemical reactions and the development of fascinating luminescent systems.
光致发光是操纵光能最精细的方法之一。典型的光致发光发射体大多是稳定物质，具有从激发态自发发射光子的纯光物理过程。中间发射体难以捉摸，这归因于它们的同步能量转移过程，包括光物理和不完全光化学途径。含有自由基的中间发射体因其固有的化学反应性而更难被观察到。在这里，通过聚合物交联网络中自发形成的空间限制克服了这些挑战，同时捕获了化学活性中间体。这些双重态中间体在化学交联限制条件下表现出独特的长波长发射，它们的发光机制为设计具有液晶特性和对时空加密具有光响应特性的中间发射体提供了新的视角，有望用于光化学反应的检测和迷人发光系统的开发。
