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Slipped Structure of Covalent Organic Framework Facilitates Two‐Photon Adsorption for Improving Near‐Infrared Excited Fluorescence Imaging

DOI:10.1002/ange.201912594 期刊:Angewandte Chemie 出版年份:2019 更新时间:2025-09-11 14:15:04
摘要: Fluorescent materials exhibiting the characteristics of strong two-photon absorption (TPA) are extensively used for nonlinear optics, bio-imaging and phototherapy. One practical approach to obtain fluorescent materials with high TPA performance is to polymerize molecular chromophores to form π-conjugated structure. This leads to the increase in TPA cross-section per chromophore, however, efforts to towards this direction was capped by the lack of long-range ordering in the structure and the strong π-π stacking between the chromophores. Here, we reported the rational design of benzothiadiazole-based covalent organic framework (COF) for promoting TPA performance and obtaining the efficient two-photon excited fluorescence. Structure characterizations and spectroscopic studies revealed that the enhancement in TPA performance was attributed to the donor-π-acceptor-π-donor (D-π-A-π-D) configuration of the chromophore, long-range order, and large π-conjugation domain of COF crystals. The structural slipping in TPA-COF not only attenuates the π-π stacking interaction between the layers, but more importantly, overcomes the aggregation-caused emission quenching of the chromophores for improving near-infrared two-photon excited fluorescence imaging.
作者: Jin-Yue Zeng,Xiao-Shuang Wang,Bo-Ru Xie,Min-Jie Li,Xian-Zheng Zhang
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Investigating the design of benzothiadiazole-based covalent organic framework (COF) to enhance two-photon absorption (TPA) performance for improving near-infrared excited fluorescence imaging.

The study demonstrates that TPA-COF can serve as a promising candidate with efficient TPA performance by utilizing the unique crystalline feature of COF. The slipped structure, long-range crystal domain, and π-conjugation domain significantly improve the delocalization of π-electrons, leading to high dipole value and TPA activity. This work offers a pathway to overcome aggregation-caused quenching and acquire near-infrared two-photon excited COFs for future biomedical applications.

The study is limited by the specific design and synthesis of the benzothiadiazole-based COF and its application in fluorescence imaging, which may not be directly applicable to other materials or imaging techniques.

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