Chen Yahui, Lu Sheng, Abbas Abedi Syed Ali, Jeong Minseok, Li Haidong, Hwa Kim Myung, Park Sungnam, Liu Xiaogang, Yoon Juyoung, Chen Xiaoqiang
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing Tech University, 211816, Nanjing, China.
Department of Chemistry and Nanoscience, Ewha Womans University, 03760, Seoul, Korea.
Angew Chem Int Ed Engl. 2023 Oct 2;62(40):e202311543. doi: 10.1002/anie.202311543. Epub 2023 Aug 28.
Excited-state intramolecular proton transfer (ESIPT)-based solid luminescent materials with multiple hydrogen bond acceptors (HBAs) remain unexplored. Herein, we introduced a family of Janus-type ESIPT chromophores featuring distinctive hydrogen bond (H-bond) selectivity between competitive HBAs in a single molecule. Our investigations showed that the central hydroxyl group preferentially forms intramolecular H-bonds with imines in imine-modified 2-hydroxyphenyl benzothiazole (HBT) chromophores but tethers the benzothiazole moiety in hydrazone-modified HBT chromophores. Imine-derived HBTs generally exhibit higher fluorescence efficiency, while hydrazone-derived HBTs show a reduced overlap between the absorption and fluorescence bands. Quantum chemical calculations unveiled the molecular origins of the biased intramolecular H-bonds and their impact on the ESIPT process. This Janus-type ESIPT chromophore skeleton provides new opportunities for the design of solid luminescent materials.
具有多个氢键受体（HBA）的基于激发态分子内质子转移（ESIPT）的固体发光材料尚未得到探索。在此，我们引入了一类Janus型ESIPT发色团，其在单个分子中的竞争性HBA之间具有独特的氢键（H键）选择性。我们的研究表明，中心羟基优先与亚胺修饰的2-羟基苯基苯并噻唑（HBT）发色团中的亚胺形成分子内H键，但在腙修饰的HBT发色团中与苯并噻唑部分相连。亚胺衍生的HBT通常表现出更高的荧光效率，而腙衍生的HBT在吸收和荧光带之间的重叠减少。量子化学计算揭示了偏向分子内H键的分子起源及其对ESIPT过程的影响。这种Janus型ESIPT发色团骨架为固体发光材料的设计提供了新的机会。
