文献类型：期刊文献

英文题名：Enhancing the deep-red/near-infrared fluorescence of higher rylene diimides via the chalcogen-annulation strategy

作者：Chen, Kai[1,2];Chen, Xiao[3];Hu, Ke[4];Zhao, Yilun[1,2];Liu, Yujian[3];Liu, Guogang[1,2];Chen, Jinquan[4];Jiang, Wei[1,2,3];Shuai, Zhigang[3];Qu, Da-Hui[1,2];Wang, Zhaohui[1,2,3]

机构：[1]East China Univ Sci & Technol, Frontiers Sci Ctr Materiobiol & Dynam Chem, Feringa Nobel Prize Scientist Joint Res Ctr, Sch Chem & Mol EngnKey Lab Adv Mat,Inst Fine Chem, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem,Inst Fi, Sch Chem & Mol Engn,Joint Int Res Lab Precis Chem, Shanghai 200237, Peoples R China;[3]Tsinghua Univ, Dept Chem, Key Lab Organ Optoelect & Mol Engn, Beijing, Peoples R China;[4]East China Normal Univ, State Key Lab Precis Spect, 500 Dongchuan Rd, Shanghai 200241, Peoples R China

年份：2024

卷号：67

期号：4

起止页码：1324

外文期刊名：SCIENCE CHINA-CHEMISTRY

收录：;EI(收录号：20240315385719);WOS:【SCI-EXPANDED(收录号:WOS:001142350700001)】；

基金：This work was financially supported by the National Natural Science Foundation of China (NSFC) (22235005), the National Postdoctoral Program for Innovative Talents (BX20200128), the 69th batch of Chinese postdoctoral general support (2021M691004), Shanghai Municipal Science and Technology Major Project (2018SHZDZX03) and the Fundamental Research Funds for the Central Universities, the Programme of Introducing Talents of Discipline to Universities (B16017). We acknowledge Prof. He Tian from East China University of Science and Technology for the constructive guidance.

语种：英文

外文关键词：pi-extended rylene diimides; chalcogen-annulation strategy; deep-red/near-infrared fluorescence

摘要：Deep-red/near-infrared fluorescence is highly suitable for bioimaging owing to its ability to deeply penetrate tissues, organs, and live animals. However, developing organic fluorophores with high deep-red/near-infrared fluorescence quantum yield (phi(FL)) and fluorescent brightness remain a significant challenge owing to the energy gap law. Herein, we developed a straightforward and effective chalcogen-annulation strategy by introducing O, S and Se into the bay region of TDI and QDI fluorophores, realizing the increase of phi(FL) and fluorescent brightness up to 10 times. To our best knowledge, this study potentially stands as the pioneering instance showcasing the anti-heavy-atom effect of chalcogens, and the absolute phi(FL) (93%) and fluorescent brightness (128,200 cm(-1) mol(-1) L) of Se-TDI is among top deep-red/near-infrared organic fluorophores currently available. The femtosecond transient absorption (fs-TA) measurements show the absence of obvious changes of the excited state lifetime after the introduction of chalcogens in TDI and QDI fluorophores, indicating that intersystem crossing (ISC) can be neglected in TDI and QDI fluorophores. Theoretical calculations further reveal the chalcogen-annulation strategy increase the radiative rates and reduce the reorganization energy of several accepting modes at the ground state in TDI fluorophores, leading to the suppression of internal conversion (IC) processes. Our chalcogen-annulation strategy, which effectively increases the phi(FL) and restricts the IC processes, while remaining unaffected by the heavy-atom effect, offers novel insights and theoretical support for the design and synthesis of deep-red/near-infrared organic fluorophores with high phi(FL) and fluorescent brightness.