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Orthogonal carbazole-perylene bisimide pentad: a photoconversion-tunable photosensitizer with diversified excitation and excited-state relaxation pathways

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Abstract

Integrating multiple photosensitive properties into an “all-in-one” photosensitizer (PS) shows great promise for the treatment of cancers owing to synergistic effect among them. However, the development of such PSs, especially those that need a single laser source, remains a challenge. Herein, we report an orchestration of electron donors and acceptors in a propeller-like pentad, PBI-4Cz, where four carbazole (Cz) units are covalently linked to the ortho-positions of the perylene bisimide (PBI) core. Strong intramolecular donor-acceptor interaction significantly quenches the luminescence and largely extends the absorption spectra to near-infrared region. Excited-state dynamics investigated via femto- and nano-second transient absorption spectroscopy revealed exclusive charge separation of the PBI-4Cz within initial 0.5 ps when photoexcited regardless of which intermediate is involved. Energy dissipation of the resulting charge-separated state (PBI•−-4Cz•−) is subjected to the toggle between intersystem-crossing toward excited triplet states and charge recombination toward ground states. Relative importance of the two pathways can be tuned by micro-environmental polarity, which endows PBI-4Cz remarkable performances of singlet-oxygen generation (>90.0%) in toluene and photothermal conversion (∼28.6%) in DMSO. Harnessing intrinsic photostability and excited-state processes of heavy-atom-free PBI derivatives not only holds a promise for multifunctional phototheranostics, but also provides a prototype for designing high-performance PSs with tunable photoconversion pathways.

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Acknowledgements

This work was supported by the Natural Science Foundation of China (21820102005, 22132002), 111 project (B14041), the Fundamental Research Funds for the Central Universities of China (2019TS033, GK202001005 and GK202003034) and the Youth Innovation Team of Shaanxi Universities. We thank Dr. Junxue Liu and Dr. Shiping Wang for helps in measurements of transient absorption spectra, Manping Qian for measurements of cyclic voltammetry, Prof. Xiaobing Wang for helpful discussion on photosensitive properties of PBI-4Cz and Dr. Hongyue Wang for helpful discussions on the analysis of TAS data.

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Authors and Affiliations

  1. Key Laboratory of Applied Surface and Colloid Chemistry of Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an, 710119, China

    Zhaolong Wang, Simin Lin, Gang Wang, Xingmao Chang, Xinyu Gou, Taihong Liu & Yu Fang

  2. College of Life Sciences, Shaanxi Normal University, Xi’an, 710119, China

    Yue Sun

  3. State Key Laboratory of Molecular Reaction Dynamics and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China

    Shengye Jin

  4. Frontier Institute of Science and Technology, Xi’an Jiaotong University, Xi’an, 710054, China

    Gang He

  5. Department of Chemistry, Taiwan University, Taipei, 10617, China

    Yu-Chen Wei & Pi-Tai Chou

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  1. Zhaolong Wang
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  2. Yue Sun
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  3. Simin Lin
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  4. Gang Wang
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  9. Gang He
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  10. Yu-Chen Wei
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Correspondence to Taihong Liu or Yu Fang.

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Orthogonal carbazole-perylene bisimide pentad: photoconversion-tunable photosensitizer with diversified excitation and excited-state relaxation pathways

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Wang, Z., Sun, Y., Lin, S. et al. Orthogonal carbazole-perylene bisimide pentad: a photoconversion-tunable photosensitizer with diversified excitation and excited-state relaxation pathways. Sci. China Chem. 64, 2193–2202 (2021). https://doi.org/10.1007/s11426-021-1154-0

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  • DOI: https://doi.org/10.1007/s11426-021-1154-0

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