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ACQ-to-AIE Transformation: Tuning Molecular Packing by Regioisomerization for Two-Photon NIR Bioimaging
Authors:Dr Yuanyuan Li  Dr Shunjie Liu  Huwei Ni  Haoke Zhang  Dr Hequn Zhang  Clarence Chuah  Chao Ma  Prof Kam Sing Wong  Prof Jacky W Y Lam  Prof Ryan T K Kwok  Prof Jun Qian  Prof Xuefeng Lu  Prof Ben Zhong Tang
Institution:1. Department of Chemistry, Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, Institute for Advanced Study, Department of Chemical and Biological Engineering, State Key Laboratory of Molecular Neuroscience and Division of Life Science, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China

HKUST-Shenzhen Research Institute, No. 9 Yuexing 1st RD, South Area, Hi-tech Park, Nanshan, Shenzhen, 518057 China

These authors contributed equally to this work.;2. Department of Chemistry, Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, Institute for Advanced Study, Department of Chemical and Biological Engineering, State Key Laboratory of Molecular Neuroscience and Division of Life Science, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China

These authors contributed equally to this work.;3. State Key Laboratory of Modern Optical Instrumentations, Centre for Optical and Electromagnetic Research, College of Optical Science and Engineering, Zhejiang University, Hangzhou, 310058 China

These authors contributed equally to this work.;4. Department of Chemistry, Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, Institute for Advanced Study, Department of Chemical and Biological Engineering, State Key Laboratory of Molecular Neuroscience and Division of Life Science, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China;5. State Key Laboratory of Modern Optical Instrumentations, Centre for Optical and Electromagnetic Research, College of Optical Science and Engineering, Zhejiang University, Hangzhou, 310058 China

Interdisciplinary Institute of Neuroscience and Technology (ZIINT), the Second Affiliated Hospital, School of Medicine, Zhejiang University, Hangzhou, 310020 China;6. Department of Physics, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China;7. Department of Chemistry, Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, Institute for Advanced Study, Department of Chemical and Biological Engineering, State Key Laboratory of Molecular Neuroscience and Division of Life Science, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China

HKUST-Shenzhen Research Institute, No. 9 Yuexing 1st RD, South Area, Hi-tech Park, Nanshan, Shenzhen, 518057 China;8. State Key Laboratory of Modern Optical Instrumentations, Centre for Optical and Electromagnetic Research, College of Optical Science and Engineering, Zhejiang University, Hangzhou, 310058 China;9. Department of Materials Science, Fudan University, Shanghai, 200438 China

Abstract:The traditional design strategies for highly bright solid-state luminescent materials rely on weakening the intermolecular π–π interactions, which may limit diversity when developing new materials. Herein, we propose a strategy of tuning the molecular packing mode by regioisomerization to regulate the solid-state fluorescence. TBP-e-TPA with a molecular rotor in the end position of a planar core adopts a long-range cofacial packing mode, which in the solid state is almost non-emissive. By shifting molecular rotors to the bay position, the resultant TBP-b-TPA possesses a discrete cross packing mode, giving a quantum yield of 15.6±0.2 %. These results demonstrate the relationship between the solid-state fluorescence efficiency and the molecule's packing mode. Thanks to the good photophysical properties, TBP-b-TPA nanoparticles were used for two-photon deep brain imaging. This molecular design philosophy provides a new way of designing highly bright solid-state fluorophores.
Keywords:ACQ-to-AIE transformation  aggregation-induced emission  cross packing  regioisomerization  two-photon imaging
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