Yuan Mengjia, Ma Fuyin, Chen Lixi, Li Baoyu, Dai Xing, Shu Jie, He Linwei, Chen Junchang, Lin Shujing, Xie Guohua, Chai Zhifang, Wang Shuao
State Key Laboratory of Radiation Medicine and Protection, School for Radiological and Interdisciplinary Sciences (RAD-X) and Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions, Soochow University, Suzhou 215123, China.
The Institute of Flexible Electronics (Future Technologies), Xiamen University, Xiamen 361005, China.
J Am Chem Soc. 2024 Jan 17;146(2):1250-1256. doi: 10.1021/jacs.3c10511. Epub 2024 Jan 8.
Luminescent covalent organic frameworks (LCOFs) have emerged as indispensable candidates in various applications due to their greater tunable emitting properties and structural robustness compared to small molecule emitters. An unsolved issue in this area is developing highly luminescent LCOFs of which the nonradiative quenching pathways were suppressed as much as possible. Here, a robust aminal-linked COF (DD-COF) possessing perdeuterated light-emitting monomers was designed and synthesized. The solid-state photoluminescence quantum yield of the DD-COF reaches 81%, significantly outcompeting all state-of-the-art LCOFs reported so far. The exceptional luminescent efficiency is attributed to the inhibition of different pathways of nonradiative decay, especially from bond vibrations where only substitution by a heavier isotope with a lower zero-point vibration frequency works. Furthermore, the prepared deuterated COF not only boosts higher photostability under UV irradiation but also enables superior fluorescence sensing performance for iodine detection compared to nondeuterated COF.
发光共价有机框架（LCOF）由于其与小分子发光体相比具有更大的可调发射特性和结构稳健性，已成为各种应用中不可或缺的候选材料。该领域一个尚未解决的问题是开发高发光LCOF，其非辐射猝灭途径应尽可能受到抑制。在此，设计并合成了一种具有全氘代发光单体的稳健氨基连接COF（DD-COF）。DD-COF的固态光致发光量子产率达到81%，明显优于迄今为止报道的所有先进LCOF。这种卓越的发光效率归因于对不同非辐射衰变途径的抑制，特别是来自键振动的途径，只有用具有较低零点振动频率的较重同位素进行取代才能起作用。此外，所制备的氘代COF不仅在紫外线照射下具有更高的光稳定性，而且与非氘代COF相比，在碘检测方面具有卓越的荧光传感性能。
