Rational Design of NIR-II AIEgens with Ultrahigh Quantum Yields for Photo- and Chemiluminescence Imaging

化学 量子产额 化学发光 光化学 三苯胺 光致发光 四苯乙烯 荧光 猝灭(荧光) 光电子学 聚集诱导发射 物理化学 光学 材料科学 物理
作者
Hanchen Shen,Feiyi Sun,Xinyan Zhu,Jianyu Zhang,Xinwen Ou,Jianquan Zhang,Changhuo Xu,Herman H. Y. Sung,Ian D. Williams,Sijie Chen,Ryan T. K. Kwok,Jacky W. Y. Lam,Jianwei Sun,Fan Zhang,Ben Zhong Tang
出处
期刊:Journal of the American Chemical Society [American Chemical Society]
卷期号:144 (33): 15391-15402 被引量:144
标识
DOI:10.1021/jacs.2c07443
摘要

Fluorescence imaging in the second near-infrared window (NIR-II, 1000-1700 nm) using small-molecule dyes has high potential for clinical use. However, many NIR-II dyes suffer from the emission quenching effect and extremely low quantum yields (QYs) in the practical usage forms. The AIE strategy has been successfully utilized to develop NIR-II dyes with donor-acceptor (D-A) structures with acceptable QYs in the aggregate state, but there is still large room for QY improvement. Here, we rationally designed a NIR-II emissive dye named TPE-BBT and its derivative (TPEO-BBT) by changing the electron-donating triphenylamine unit to tetraphenylethylene (TPE). Their nanoparticles exhibited ultrahigh relative QYs of 31.5% and 23.9% in water, respectively. By using an integrating sphere, the absolute QY of TPE-BBT nanoparticles was measured to be 1.8% in water. Its crystals showed an absolute QY of 10.4%, which is the highest value among organic small molecules reported so far. The optimized D-A interaction and the higher rigidity of TPE-BBT in the aggregate state are believed to be the two key factors for its ultrahigh QY. Finally, we utilized TPE-BBT for NIR-II photoluminescence (PL) and chemiluminescence (CL) bioimaging through successive CL resonance energy transfer and Förster resonance energy transfer processes. The ultrahigh QY of TPE-BBT realized an excellent PL imaging quality in mouse blood vessels and an excellent CL imaging quality in the local arthrosis inflammation in mice with a high signal-to-background ratio of 130. Thus, the design strategy presented here brings new possibilities for the development of bright NIR-II dyes and NIR-II bioimaging technologies.
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