水中分散的有机长效发光材料

doi:10.6023/cjoc202604002

有机化学 ›› 2026, Vol. 46 ›› Issue (9): 3688-3696.DOI: 10.6023/cjoc202604002 上一篇下一篇

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^,^*()

^a 常州大学材料科学与工程学院江苏常州 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 发布日期:2026-07-14
作者简介:
^† 共同第一作者.
基金资助:
国家自然科学基金(22475228); 国家自然科学基金(22175194)

Organic Long Persistent Luminescence Materials in Aqueous Medium

Qianhui Chong^a^,^b^,^†, Guangming Wang^b^,^†, Guoyi Wu^b, Qianqian Yan^b, Biaobing Wang^a^,^*(), Kaka Zhang^b^,^*()

^a School of Materials Science and Engineering, Changzhou University, Changzhou, Jiangsu 213100
^b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai 200032

Received:2026-04-01 Revised:2026-05-27 Published:2026-07-14
Contact:
^* E-mail: zhangkaka@sioc.ac.cn;
biaobing@cczu.edu.cn
About author:
Dedicated to the 100th anniversary of the birth of Professor Xikui Jiang.
^† These authors contributed equally to this work
Supported by:
National Natural Science Foundation of China(22475228); National Natural Science Foundation of China(22175194)

文章分享

1. 263688S.pdf.pdf(8973KB)

摘要/Abstract

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. 通过供体-敏化剂-受体(DSA)三组分策略, 制备了水性OLPL分散体系. 将二氟化硼β-二酮(BF₂bdk, 光敏剂)、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 ℃), 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. A aqueous OLPL system was successfully prepared 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-methoxy- phenyl benzoate (MeOPhB), which serves both as the acceptor and a crystalline host matrix. Taking advantage of the moderate melting point (74 ℃) 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 state, thermally activated delayed fluorescence

引用此文

种千惠, 王光明, 吴国伊, 闫倩倩, 王标兵, 张卡卡. 水中分散的有机长效发光材料[J]. 有机化学, 2026, 46(9): 3688-3696.

Qianhui Chong, Guangming Wang, Guoyi Wu, Qianqian Yan, Biaobing Wang, Kaka Zhang. Organic Long Persistent Luminescence Materials in Aqueous Medium[J]. Chinese Journal of Organic Chemistry, 2026, 46(9): 3688-3696.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 6

图式1. BF2bdk化合物的合成方法及TMB、BF2bdk和MeOPhB的化学结构式

Scheme 1. Synthesis process of BF2bdk, and (b) chemical structures of BF2bdk, MeOPhB, and TMB

图1. (a) BF2bdk-MeOPhB材料在365 nm光激发时及停止激发后的照片、(b)室温下BF2bdk-MeOPhB材料的稳态光谱与延迟光谱(1 ms延迟)、(c)室温下BF2bdk-MeOPhB材料的寿命衰减曲线和(d) 365 nm激发下BF2bdk-MeOPhB的变温延迟光谱(1 ms延迟)

Figure 1. (a) Photographs of BF2bdk-MeOPhB under 365 nm UV light excitation and after the light source was stopped, (b) room-temperature steady-state and delayed emission spectra (1 ms delay) of BF2bdk-MeOPhB materials, (c) room-temperature emission decay of BF2bdk-MeOPhB materials, and (d) variable-temperature delayed emission spectra (1 ms delay) of BF2bdk-MeOPhB materials excited at 365 nm

图2. (a) TMB-BF2bdk-MeOPhB材料在365 nm光激发时及停止激发后的照片; (b) 365 nm激发和室温下TMB-BF2bdk-MeOPhB材料的稳态光谱与延迟光谱; (c) 365 nm激发后TMB-BF2bdk-MeOPhB材料在不同延迟时间下的OLPL光谱; (d) 365 nm激发下TMB-BF2bdk-MeOPhB材料发光衰减曲线; (e) 365 nm激发下TMB-BF2bdk-MeOPhB材料的OLPL衰减曲线对数图

Figure 2. (a) Photographs of TMB-BF2bdk-MeOPhB under 365 nm UV light excitation and after the light source was stopped; (b) Room-temperature steady-state and delayed emission spectra (1 ms delay) of TMB-BF2bdk-MeOPhB materials excited at 365 nm; (c) OLPL spectra of TMB-BF2bdk-MeOPhB materials at different delay times; (d) Room-temperature emission decay of TMB-BF2bdk-Me- OPhB materials excited at 365 nm; (e) OLPL intensity of TMB-BF2bdk-MeOPhB materials as a function of delay time (excited at 365 nm)

图3. (a) TMB-BF2bdk-MeOPhB材料在420 nm光激发时及停止激发后的照片; (b) 420 nm激发和室温下TMB-BF2bdk-MeOPhB材料的稳态光谱与延迟光谱; (c) 420 nm激发后TMB-BF2bdk-MeOPhB材料在不同延迟时间下的OLPL光谱; (d) 420 nm激发下TMB-BF2bdk-MeOPhB材料发光衰减曲线; (e) 420 nm激发下TMB-BF2bdk-MeOPhB材料的OLPL衰减曲线对数图

Figure 3. (a) Photographs of TMB-BF2bdk-MeOPhB under 420 nm light excitation and after the light source was stopped; (b) room- temperature steady-state and delayed emission spectra (1 ms delay) of TMB-BF2bdk-MeOPhB materials excited at 420 nm; (c) OLPL spectra of TMB-BF2bdk-MeOPhB materials at different delay times; (d) room-temperature emission decay of TMB-BF2bdk-MeOPhB materials excited at 420 nm; (e) OLPL intensity of TMB-BF2bdk-MeOPhB materials as a function of delay time (excited at 420 nm)

图4. 三组分高性能OLPL材料光物理机制示意图

Figure 4. Schematic illustration of the afterglow mechanism in three-component high-performance OLPL materials

图6. (a) TMB-BF2bdk-MeOPhB水相分散液在365 nm紫外灯激发下和停止激发后的照片; (b) TMB-BF2bdk-MeOPhB水相分散液的显微镜照片; (c) TMB-BF2bdk-MeOPhB水相分散液注射到鱼体内后在365 nm紫外灯激发下和停止激发后的照片; (d)室温下TMB-BF2bdk-MeOPhB水相分散液的稳态发射光谱和延迟发射光谱(1 ms延迟); (e) 365 nm激发后TMB-BF2bdk-MeOPhB水相分散液在不同延迟时间下的发射光谱; (f)用光谱荧光显微镜系统检测到的OLPL水分散体的余辉信号

Figure 6. (a) Photographs of TMB-BF2bdk-MeOPhB aqueous dispersion under 365 nm UV light excitation and after the removal of the UV light; (b) Microscope image of TMB-BF2bdk-MeOPhB aqueous dispersion; (c) Photographs of living fish injected TMB-BF2bdk- MeOPhB aqueous dispersion under 365 nm UV lamp excitation and after ceasing the light source; (d) Room-temperature steady-state and delayed emission spectra (1 ms delay) of TMB-BF2bdk-MeOPhB aqueous dispersion; (e) Delayed emission spectra of TMB-BF2bdk- MeOPhB aqueous dispersion at different delayed times after excitation with a 365 nm lamp; (f) Afterglow signal of the OLPL aqueous dispersion detected by spectroscopy fluorescence microscope system

参考文献 52

[1]	Yam, V. W.-W.; Au, V. K.-M.; Leung, S. Y.-L. Chem. Rev. 2015, 115, 7589.
[2]	Gan, N.; Shi, H.; An, Z.; Huang, W. Adv. Funct. Mater. 2018, 28, 1802657.
[3]	Kenry, ; Chen, C.; Liu, B. Nat. Commun. 2019, 10, 2111.
[4]	Zhao, W.; He, Z.; Tang, B. Z. Nat. Rev. Mater. 2020, 5, 869.
[5]	Yang, X.; Waterhouse, G. I. N.; Lu, S.; Yu, J. Chem. Soc. Rev. 2023, 52, 8005.
[6]	Kabe, R.; Adachi, C. Nature 2017, 550, 384.
[7]	Ma, X.; Wang, J.; Tian, H. Acc. Chem. Res. 2019, 52, 738.
[8]	Forni, A.; Lucenti, E.; Botta, C.; Cariati, E. J. Mater. Chem. C 2018, 6, 4603.
[9]	Hirata, S. Adv. Opt. Mater. 2017, 5, 1700116.
[10]	Li, Q.; Li, Z. Acc. Chem. Res. 2020, 53, 962.
[11]	Zhang, T.; Ma, X.; Wu, H.; Zhu, L.; Zhao, Y.; Tian, H. Angew. Chem., Int. Ed. 2020, 59, 11206.
[12]	Gao, H.; Ma, X. Aggregate 2021, 2, e38.
[13]	Guo, S.; Dai, W.; Chen, X.; Lei, Y.; Shi, J.; Tong, B.; Cai, Z.; Dong, Y. ACS Mater. Lett. 2021, 3, 379.
[14]	Singh, M.; Liu, K.; Qu, S.; Ma, H.; Shi, H.; An, Z.; Huang, W. Adv. Opt. Mater. 2021, 9, 2002197.
[15]	Hirata, S. Appl. Phys. Rev. 2022, 9, 011304.
[16]	Yan, X.; Peng, H.; Xiang, Y.; Wang, J.; Yu, L.; Tao, Y.; Li, H.; Huang, W.; Chen, R. Small 2022, 18, 2104073.
[17]	Zhou, Q.; Yang, C.; Zhao, Y. Chem 2023, 9, 2446.
[18]	Ding, B.; Ma, X.; Tian, H. Acc. Mater. Res. 2023, 4, 827.
[19]	Wu, K.; Liu, D.; Zhu, L.; Wu, T.; Xu, Y.; He, C.; Xiong, Y.; Zhao, Z.; Tang, B. Z. Commun. Chem. 2025, 8, 85.
[20]	Zheng, H.; Zhang, Z.; Cai, S.; An, Z.; Huang, W. Adv. Mater. 2024, 36, 2311922.
[21]	Ren, J.; Wang, Y.; Tian, Y.; Liu, Z.; Xiao, X.; Yang, J.; Fang, M.; Li, Z. Angew. Chem., Int. Ed. 2021, 60, 12335.
[22]	Zhou, W.-L.; Chen, Y.; Yu, Q.; Zhang, H.; Liu, Z.-X.; Dai, X.-Y.; Li, J.-J.; Liu, Y. Nat. Commun. 2020, 11, 4655.
[23]	Zhen, X.; Tao, Y.; An, Z.; Chen, P.; Xu, C.; Chen, R.; Huang, W.; Pu, K. Adv. Mater. 2017, 29, 1606665.
[24]	Wang, X.-F.; Xiao, H.; Chen, P.-Z.; Yang, Q.-Z.; Chen, B.; Tung, C.-H.; Chen, Y.-Z.; Wu, L.-Z. J. Am. Chem. Soc. 2019, 141, 5045.
[25]	Cao, P.; Chen, Q.; Wu, P. Chin. J. Chem. 2023, 41, 979.
[26]	Sun, H.; Zhu, L. Aggregate 2023, 4, e253.
[27]	Wang, Y.; Gao, H.; Yang, J.; Fang, M.; Ding, D.; Tang, B. Z.; Li, Z. Adv. Mater. 2021, 33, 2007811.
[28]	Liu, J.; Sun, Y.; Wang, G.; Chen, X.; Li, J.; Wang, X.; Zou, Y.; Wang, B.; Zhang, K. Adv. Opt. Mater. 2022, 10, 2201502.
[29]	Wang, J.; Huang, Z.; Ma, X.; Tian, H. Angew. Chem., Int. Ed. 2020, 59, 9928.
[30]	Jinnai, K.; Kabe, R.; Adachi, C. Adv. Mater. 2018, 30, 1800365.
[31]	Lin, Z.; Kabe, R.; Nishimura, N.; Jinnai, K.; Adachi, C. Adv. Mater. 2018, 30, 1803713.
[32]	Alam, P.; Leung, N. L. C.; Liu, J.; Cheung, T. S.; Zhang, X.; He, Z.; Kwok, R. T. K.; Lam, J. W. Y.; Sung, H. H. Y.; Williams, I. D.; Chan, C. C. S.; Wong, K. S.; Peng, Q.; Tang, B. Z. Adv. Mater. 2020, 32, 2001026.
[33]	Lin, Z.; Kabe, R.; Wang, K.; Adachi, C. Nat. Commun. 2020, 11, 191.
[34]	Nishimura, N.; Lin, Z.; Jinnai, K.; Kabe, R.; Adachi, C. Adv. Funct. Mater. 2020, 30, 2000795.
[35]	Tan, S.; Jinnai, K.; Kabe, R.; Adachi, C. Adv. Mater. 2021, 33, 2008844.
[36]	Jinnai, K.; Kabe, R.; Lin, Z.; Adachi, C. Nat. Mater. 2022, 21, 338.
[37]	Wang, G.; Chen, X.; Li, X.; Zeng, Y.; Zhang, K. Chem. Sci. 2023, 14, 8180.
[38]	Xie, G.; Zeng, M.; Zhang, X.; Luo, A.; Zhang, J.; He, F.; Wang, X.; Hu, Y.; Wang, W.; Xie, Y.; Li, H.; Chen, R.; Tao, Y. Sci. China Mater. 2023, 66, 4756.
[39]	Wang, X.; Li, J.; Zeng, Y.; Chen, X.; Wu, M.; Wang, G.; Li, X.; Wang, B.; Zhang, K. Chem. Eng. J. 2023, 460, 141916.
[40]	Alam, P.; Cheung, T. S.; Leung, N. L. C.; Zhang, J.; Guo, J.; Du, L.; Kwok, R. T. K.; Lam, J. W. Y.; Zeng, Z.; Phillips, D. L.; Sung, H. H. Y.; Williams, I. D.; Tang, B. Z. J. Am. Chem. Soc. 2022, 144, 3050.
[41]	Li, W.; Li, Z.; Si, C.; Wong, M. Y.; Jinnai, K.; Gupta, A. K.; Kabe, R.; Adachi, C.; Huang, W.; Zysman‐Colman, E.; Samuel, I. D. W. Adv. Mater. 2020, 32, 2003911.
[42]	Liang, X.; Zheng, Y.; Zuo, J. Angew. Chem., Int. Ed. 2021, 60, 16984.
[43]	Wang, G.; Chen, X.; Zeng, Y.; Li, X.; Wang, X.; Zhang, K. J. Am. Chem. Soc. 2024, 146, 24871.
[44]	Xia, W.; Ye, Z.; Wu, G.; Yao, H.; Gao, H.; Xu, B.; Chong, Q.; Zhang, K. Angew. Chem., Int. Ed. 2025, e202518387.
[45]	Zeng, Y.; Wang, G.; Gao, H.; Chen, X.; Piao, X.; Li, Y.; Tan, X.; Chan, C.-Y.; Wang, B.; Zhang, K. CCS Chem. 2025, 8, 1672.
[46]	Gao, H.; Wang, G.; Wang, T.; Ye, Z.; Yan, Q.; Chong, Q.; Chan, C.; Wang, B.; Zhang, K. Adv. Sci. 2025, 12, 2416853.
[47]	Ye, Z.; Xia, W.; Wang, G.; Wu, G.; Gao, H.; Xu, B.; Zhang, K. Adv. Sci. 2025, 12, e01558.
[48]	Li, J.; Wang, X.; Zhao, X.; Chen, X.; Ding, S.; Wu, M.; Zhang, K. Chin. J. Chem. 2022, 40, 2507.
[49]	Wang, X.; Yan, S.; Wang, G.; Li, J.; Li, X.; Zhang, K. Angew. Chem., Int. Ed. 2021, 60, 17138.
[50]	Yao, H.; Zhang, Y.; Wang, G.; Li, J.; Huang, J.; Wang, X.; Zhang, Z.; Chen, Li.; Pan, Z.; Zhang, Z. ACS Appl. Nano Mater. 2023, 6, 15138.
[51]	Luo, T.; Xiao, Y.; Li, X.; Xia, W.; Zhang, K. Chin. J. Org. Chem. 2025, 45, 4202 (in Chinese).
	(罗婷, 肖宇峰, 李珣, 夏雯, 张卡卡, 有机化学, 2025, 45, 4202.)
[52]	Xu, B.; Wang, G.; Gao, H.; Wang, T.; Ye, Z.; Xia, W.; Chong, Q.; Yan, Q.; Zhang, K. Chem. Eng. J. 2025, 514, 163359.

水中分散的有机长效发光材料

Organic Long Persistent Luminescence Materials in Aqueous Medium

RichHTML

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

图/表 6

参考文献 52

相关文章 11

编辑推荐

相关统计

本文评价

[1]	张梦媛, 袁之敏. 多功能圆偏振发光有机小分子[J]. 有机化学, 2026, 46(5): 1871-1882.
[2]	高玉兰, 龙江琴, 王秋生. 9-芴基甲氧基羰基-酪氨酸掺杂聚乙烯醇室温磷光薄膜性质研究[J]. 有机化学, 2025, 45(4): 1261-1267.
[3]	吴建荣, 宋敏, 刘釜铭, 周东营, 廖良生, 蒋佐权. 双功能修饰策略构建蓝光发射的硼基多重共振热激活延迟荧光材料[J]. 有机化学, 2025, 45(11): 4152-4162.
[4]	罗婷, 肖宇峰, 李珣, 夏雯, 张卡卡. 基于分子内电荷转移技术构建高效热激活延迟荧光型有机余辉材料[J]. 有机化学, 2025, 45(11): 4202-4209.
[5]	李楠, 王雲生, 李振. 三苯胺-吩噻嗪衍生物掺杂聚合物的光诱导室温磷光[J]. 有机化学, 2024, 44(8): 2487-2494.
[6]	黄凯航, 尹理, 姜青云, 汪乾, 石光, 许炳佳. 具有聚集诱导发光性质的高效热激活延迟荧光材料用于脂滴成像[J]. 有机化学, 2024, 44(8): 2479-2486.
[7]	张惟, 李庚辰, 苏昊, 戴文博, 孙鹏, 石建兵, 佟斌, 蔡政旭, 董宇平. 基于主客体掺杂室温磷光材料的氧气传感材料[J]. 有机化学, 2024, 44(8): 2523-2529.
[8]	崔怡静, 朱天文, 张强, 袁望章. 共晶提升纯有机材料室温磷光余辉性能[J]. 有机化学, 2024, 44(8): 2588-2594.
[9]	严子昂, 邹雷, 马骧. 纯有机超分子发光材料的研究进展[J]. 有机化学, 2020, 40(7): 1814-1822.
[10]	张亮, 李猛, 高庆宇, 陈传峰. 基于卤素取代邻苯二甲酰亚胺新型有机发光材料的合成及其性能研究[J]. 有机化学, 2020, 40(2): 516-520.
[11]	郑月游, 谢琼琳, 王炳喜. 10-甲基-10H-吩噻嗪-5,5-二氧化物衍生物的合成及其光物理和电化学性质[J]. 有机化学, 2016, 36(4): 803-811.