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掺杂诱导的氢键网络介观组装及其磷光寿命调控

徐成硕1,武桐玥1,管伟江1,吕超1,2
  

  1. 1. 北京化工大学化工资源有效利用全国重点实验室 2. 郑州大学化学学院,平原实验室

  • 收稿日期:2025-12-24 修回日期:2026-01-26 网络首发:2026-02-21 发布日期:2026-02-21
  • 通讯作者: 吕超 E-mail:luchao@mail.buct.edu.cn
  • 基金资助:
    国家自然科学基金(批准号:22534007, 22422401, 22374007, U22A20397, 22402006)资助

Doping-Induced Mesoscopic Assembly in Hydrogen-Bonded Networks for Phosphorescence Lifetime Modulation

XU Chengshuo1, WU Tongyue1, GUAN Weijiang1*, LU Chao1,2*   

  1. 1. State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology 2. Pingyuan Laboratory, College of Chemistry, Zhengzhou University

  • Received:2025-12-24 Revised:2026-01-26 Online First:2026-02-21 Published:2026-02-21
  • Supported by:
    Supported by the National Natural Science Foundation of China (Nos. 22534007, 22422401, 22374007, U22A20397, 22402006)

摘要: 室温磷光(RTP)因其长发光寿命、大斯托克斯位移和对环境的敏感性,在生物成像、照明显示和防伪等领域具有重要的应用前景. 氢键网络能够有效抑制非辐射跃迁、稳定三重态激发态,是固态RTP材料设计中的常用策略,但其磷光寿命的有效调控仍然具有挑战性. 基于羧酸–氨基氢键相互作用,本研究以三聚氰胺-间苯二甲酸(MA-IPA)为氢键网络构筑单元,通过引入不同羧酸取代数目的苯类小分子对组装过程进行调控. 研究结果表明,掺杂小分子并未改变MA-IPA氢键网络基本构筑单元,但显著影响了其有序堆积方式与介观结构特征,从而调节组装体的颗粒尺寸与比表面积,改变空气中氧分子对三重态激子的猝灭程度. 由此构筑的系列材料在室温下均表现出稳定的磷光发射,其磷光寿命最长可达1.7 s. 本研究为长寿命RTP材料的结构设计提供了新的思路.

关键词: 室温磷光, 氢键网络, 磷光寿命, 分子掺杂

Abstract: Room-temperature phosphorescence (RTP) has been attracting attention in recent years due to its long light-emitting lifetime, large Stokes shift, and sensitivity to the environment, which have important application prospects in the fields of bio-imaging, illumination display, and anti-counterfeiting. Hydrogen-bonded networks are widely employed in the design of solid-state RTP materials owing to their ability to suppress nonradiative transitions and stabilize triplet excited states; however, effective regulation of phosphorescence lifetimes in such systems remains challenging. In this work, a hydrogen-bonded assembly based on melamine and isophthalic acid (MA-IPA) was constructed through carboxylic acid–amine hydrogen-bond interactions, and the assembly process was modulated by introducing benzene derivatives bearing different numbers of carboxyl substituents as molecular dopants. The results show that the introduction of dopant molecules does not alter the fundamental building units of the hydrogen-bonded network of MA-IPA but significantly affects the ordered packing mode and mesoscopic structural features. As a consequence, the particle size and specific surface area of the assemblies are effectively regulated, leading to different degrees of oxygen quenching of triplet excitons under ambient conditions. The resulting materials exhibit stable RTP, with phosphorescence lifetimes of up to 1.7 s. This study provides a viable strategy for the structural regulation of long-lived RTP materials based on hydrogen-bonded networks.

Key words: room-temperature phosphorescence (RTP), hydrogen-bonded network, phosphorescence lifetime, molecular doping

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