Chen Junru, Chen Xiaojie, Cao Lei, Deng Huangjun, Chi Zhenguo, Liu Bin
Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore.
School of Chemistry, Sun Yat-sen University, Guangzhou, China.
Angew Chem Int Ed Engl. 2022 Jun 13;61(24):e202200343. doi: 10.1002/anie.202200343. Epub 2022 Apr 19.
The traditional method to achieve ultralong organic phosphorescence (UOP) is to hybrid nπ* and ππ* configurations in appropriate proportion, which are contradictory to each other for improving efficiency and lifetime of phosphorescence. In this work, through replacing the electron-donating aromatic group with a methoxy group and combining intramolecular halogen bond to promote intersystem crossing and suppress non-radiative transition, an efficient UOP molecule (2Br-OSPh) has been synthesized with the longest lifetime and brightest UOP among its isomers. As compared to CzS2Br, which has a similar substituted position of bromine atom and a larger k (the rate of intersystem crossing), the smaller ΔE (the energy gap between monomeric phosphorescence and aggregated state phosphorescence) in 2Br-OSPh could accelerate the transition from T to T *. This research indicates that both generation and accumulation of triplet excitons play an important role in realizing efficient UOP materials.
实现超长有机磷光(UOP)的传统方法是将nπ和ππ构型以适当比例混合,而这两种构型在提高磷光效率和寿命方面是相互矛盾的。在这项工作中,通过用甲氧基取代供电子芳基并结合分子内卤键来促进系间窜越并抑制非辐射跃迁,合成了一种高效的UOP分子(2Br-OSPh),它在其异构体中具有最长的寿命和最亮的UOP。与溴原子取代位置相似且k(系间窜越速率)较大的CzS2Br相比,2Br-OSPh中较小的ΔE(单体磷光与聚集态磷光之间的能隙)可以加速从T到T*的跃迁。这项研究表明,三重态激子的产生和积累在实现高效UOP材料中都起着重要作用。