有机化学    

研究论文

水中分散的有机长效发光材料

种千惠a,b#, 王光明b#, 吴国伊b, 闫倩倩b, 王标兵*,a, 张卡卡*,b   

  1. a常州大学 材料科学与工程学院 常州 213164;
    b中国科学院上海有机化学研究所 金属有机化学全国重点实验室 上海 200032
  • 收稿日期:2026-04-01 修回日期:2026-05-27
  • 作者简介:#共同第一作者
  • 基金资助:
    国家自然科学基金(No. 22475228, 22175194)资助项目.

Organic Long Persistent Luminescence Materials in Aqueous Medium

Qianhui Chonga,b,#, Guangming Wangb,#, Guoyi Wub, Yue Zhangb, Qianqian Yanb, Hongxin Gaob, Biaobing Wang*,a, Kaka Zhang*,b   

  1. aSchool of Materials Science and Engineering, Changzhou University, Changzhou, 213100;
    bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai, 200032
  • Received:2026-04-01 Revised:2026-05-27
  • Contact: *E-mail: zhangkaka@sioc.ac.cn; biaobing@cczu.edu.cn
  • About author:#equal contribution
  • Supported by:
    National Natural Science Foundation of China (No. 22475228, 22175194).

有机长效发光(OLPL)材料在生物医学领域前景广阔, 但由于水和氧的淬灭作用, 制备水性OLPL分散体系仍然具有挑战性. 本文通过供体-敏化剂-受体(DSA)三组分策略, 报道了水性OLPL分散体系. 我们将二氟化硼β-二酮(BF₂bdk)光敏剂与N,N,N',N'-四甲基联苯胺(TMB, 电子供体)和4-甲氧基苯甲酸苯酯(MeOPhB, 电子受体兼有机基质)相结合, 制备出了具有数小时余辉时长和可见光激发特性的固态OLPL材料. 利用MeOPhB适中的熔点(74°C), 该固态材料可以在表面活性剂的辅助下, 简便地加工成水性分散体系. 联用光谱的荧光显微镜证实了水性分散体系中OLPL微粒的结晶性质, 并能原位收集其发射光谱. 水性OLPL分散体保留了特征性的幂律发射衰减, 并在水中表现出显著的余辉, 这是由于结晶态的MeOPhB基质保护了电荷分离态免受淬灭. 这项工作填补了水性OLPL领域的空白, 并为将固态OLPL转化为水基体系提供了一种通用策略.

关键词: 有机长效发光, 室温磷光, 二氟化硼β-二酮, 三线态激发态, 热激活延迟荧光

The development of aqueous dispersions based on organic long-persistent luminescence (OLPL) materials is of great interest for biomedical applications, yet it is severely hindered by the quenching effects of moisture and oxygen. In this study, we demonstrate a successful aqueous OLPL system by employing a ternary donor-sensitizer-acceptor (DSA) design. Specifically, solid-state OLPL materials exhibiting hour-long afterglow and visible-light-excitable property were constructed by integrating difluoroboron β-diketonate (BF₂bdk) as the sensitizer, N,N,N',N'-tetramethylbenzidine (TMB) as the donor, and 4-methoxyphenyl benzoate (MeOPhB), which serves both as the acceptor and a crystalline host matrix. Taking advantage of the moderate melting point (74°C) of MeOPhB, these solid-state materials were efficiently converted into aqueous dispersions with the assistance of surfactants. Spectral fluorescence microscopy was utilized to verify the crystalline structure of the OLPL microparticles within the dispersion and to capture their emission spectra in situ. The resulting aqueous dispersions maintain the characteristic power-law decay of their luminescence and demonstrate remarkable stability against quenching in water. This resilience is attributed to the protective crystalline MeOPhB matrix, which effectively insulates the charge-separated states from the surrounding aqueous environment. This work not only addresses a critical gap in aqueous OLPL technology but also introduces a versatile platform for transitioning solid-state OLPL materials into water-compatible systems.

Key words: organic long persistent luminescence, room-temperature phosphorescence, difluoroboron β-diketonate, triplet excited states, thermally activated delayed fluorescence