CAS Key Laboratory of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China.
Fluorescence Research Group, Singapore University of Technology and Design, 8 Somapah Road, 487372, Singapore.
Chem Soc Rev. 2021 Nov 15;50(22):12656-12678. doi: 10.1039/d1cs00239b.
The twisted intramolecular charge transfer (TICT) mechanism has guided the development of numerous bright and sensitive fluorophores. This review briefly overviews the history of establishing the TICT mechanism, and systematically summarizes the molecular design strategies in modulating the TICT tendency of various organic fluorophores towards different applications, along with key milestone studies and representative examples. Additionally, we also succinctly review the twisted intramolecular charge shuttle (TICS) and twists during photoinduced electron transfer (PET), and compare their similarities and differences with TICT, with emphasis on understanding the structure-property relationships between the twisted geometries and how they can directly affect the fluorescence of the molecules. Such structure-property relationships presented herein will greatly aid the rational development of fluorophores that involve molecular twisting in the excited state.
扭曲的分子内电荷转移(TICT)机制指导了许多明亮和灵敏的荧光团的发展。本综述简要回顾了确立 TICT 机制的历史,并系统地总结了调节各种有机荧光团的 TICT 趋势的分子设计策略,以及关键的里程碑研究和代表性实例。此外,我们还简洁地回顾了扭曲的分子内电荷穿梭(TICS)和光诱导电子转移(PET)期间的扭转,并比较了它们与 TICT 的相似性和差异性,重点是理解扭曲几何形状与分子荧光之间的结构-性质关系,以及它们如何直接影响分子的荧光。本文介绍的这种结构-性质关系将极大地帮助涉及激发态分子扭曲的荧光团的合理发展。