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Abstract
Aggregation-induced emission (AIE) is a photophysical phenomenon correlated closely with the excited-state intramolecular motions. Although AIE has attracted increasing attention due to the significant applications in biomedical and optoelectronics, an in-depth understanding of the excited-state intramolecular motion has yet to be fully developed. Here we found the non-aromatic annulene derivative of cyclooctatetrathiophene shows typical AIE phenomenon in spite of its rotor-free structure. The underlying mechanism is investigated through photoluminescence spectra, time-resolved absorption spectra, theoretical calculations, circular dichroism as well as by pressure-dependent fluorescent spectra etc., which indicate that the aromaticity reversal from ground state to the excited state serves as a driving force for inducing the excited-state intramolecular vibration, leading to the AIE phenomenon. Therefore, aromaticity reversal is demonstrated as a reliable strategy to develop vibrational AIE systems. This work also provides a new viewpoint to understand the excited-state intramolecular motion behavior of lumiongens.
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1 Department of Chemistry, Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, Institute of Molecular Functional Materials, Division of Life Science and State Key Laboratory of Molecular Neuroscience, The Hong Kong University of Science and Technology, Hong Kong, China
2 Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, China
3 Department of Chemistry, The University of Hong Kong, Hong Kong, China; Institute of Life Sciences, Jiangsu University, Zhenjiang, China
4 Guangdong Provincial Key Laboratory of Brain Science, Disease and Drug Development, Shenzhen Research Institute, Shenzhen, China
5 Engineering Research Center for Nanomaterials, Henan University, Kaifeng, China
6 State Key Laboratory of Supramolecular Structure and Materials Jilin University, Changchun, China
7 Department of Chemistry, The University of Hong Kong, Hong Kong, China
8 Department of Chemistry, Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, Institute of Molecular Functional Materials, Division of Life Science and State Key Laboratory of Molecular Neuroscience, The Hong Kong University of Science and Technology, Hong Kong, China; Guangdong Provincial Key Laboratory of Brain Science, Disease and Drug Development, Shenzhen Research Institute, Shenzhen, China; NSFC Center for luminescence from Molecular Aggregates, SCUT-HKUST Joint Research Institute, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou, China