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A new sensitization strategy for achieving organic RTP in aqueous solution: tunable RTP and UC emission in supramolecular TTA-UC systems

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Abstract

Achieving room temperature phosphorescence (RTP) of heavy-atom-free organic molecules with near-infrared (NIR) emission in solutions is fascinating for medical and biological applications but is highly challengable. Herein, we report a new sensitization strategy to achieve RTP of heavy-atom-free fluorophores which served as energy acceptors in triplet-triplet annihilation upconversion (TTA-UC) by carefully designing the accommodated microenvironments through non-covalent interactions with a PAMAM dendrimer matrix. Sensitized RTP of a serial of diphenyl anthracene (DPA) derivatives peaked at 766 nm were observed for the first time in an aqueous solution with a maximal quantum yield of 1.4%. A ternary supramolecular assembling between the UC components and the dendrimers was formed via electrostatic interaction between the–COOH and peripheral amino groups. On one hand, it assured the efficient population of the triplet states of the fluorophore via triplet-triplet energy transfer (TTET) process; on the other hand, it restricted the motions of the fluorophores, and thus inhibited the nonradiative inactivation of the populated triplet states. These two aspects jointly contributed to the sensitized RTP of DPA units. Significantly, the microenvironment in which the annihilators resided could be regulated by adjusting the ratio of carboxyl to amino groups (–COOH/–NH2), when–COOH/–NH2 < 1, the annihilators were mainly immobilized at the periphery of the dendrimers, leading to the sensitized RTP, and when COOH/–NH2 > 1, the UC components could be partly driven to the hydrophobic cavities of the dendrimers, resulting an unprecedentedly simultaneous emission of upconverted fluorescence and down-converted phosphorescence of the annihilators.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22171194, 21971169, 92056116, 21871194, 21572142), the Science & Technology Department of Sichuan Province (2022YFH0095, 2021ZYD0052), and the Fundamental Research Funds for the Central Universities (20826041D4117). Material characterizations were performed with the support of Professor Peng Wu and Hui Wang of the Analytical & Testing Center, Sichuan University, which were greatly appreciated. We also thank Feng Yang from the Comprehensive Training Platform of the Specialized Laboratory in the College of Chemistry at Sichuan University for TEM testing.

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Authors and Affiliations

  1. Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, State Key Laboratory of Biotherapy, Sichuan University, Chengdu, 610064, China

    Lingling Wei, Fanrui Gao, Cheng He, Qiuhui He, Pengyue Jin, Yanqin Rong, Ting Zhao, Cheng Yang & Wanhua Wu

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  1. Lingling Wei
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  2. Fanrui Gao
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  3. Cheng He
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  4. Qiuhui He
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  7. Ting Zhao
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  8. Cheng Yang
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  9. Wanhua Wu
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Correspondence to Wanhua Wu.

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Supporting information The supporting information is available online at http://chem.scichina.com and http://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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A New Sensitization Strategy for Achieving Organic RTP in Aqueous Solution: Tunable RTP and UC Emission in Supramolecular TTA-UC Systems

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Wei, L., Gao, F., He, C. et al. A new sensitization strategy for achieving organic RTP in aqueous solution: tunable RTP and UC emission in supramolecular TTA-UC systems. Sci. China Chem. 66, 3546–3554 (2023). https://doi.org/10.1007/s11426-023-1786-5

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  • DOI: https://doi.org/10.1007/s11426-023-1786-5

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