华东师范大学学报(自然科学版) ›› 2023, Vol. 2023 ›› Issue (1): 73-81.doi: 10.3969/j.issn.1000-5641.2023.01.008

• 绿色功能材料 • 上一篇    下一篇

N-烷基化修饰赋予金属有机框架荧光响应功能

刘晓艳, 高恩庆*()   

  1. 华东师范大学 化学与分子工程学院 上海市绿色化学与化工过程绿色化重点实验室, 上海 200062
  • 收稿日期:2022-07-26 接受日期:2022-10-20 出版日期:2023-01-25 发布日期:2023-01-07
  • 通讯作者: 高恩庆 E-mail:eqgao@chem.ecnu.edu.cn
  • 基金资助:
    国家自然科学基金 (21971069)

N-alkylation modification of metal-organic frameworks to afford responsive fluorescence

Xiaoyan LIU, Enqing GAO*()   

  1. Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China
  • Received:2022-07-26 Accepted:2022-10-20 Online:2023-01-25 Published:2023-01-07
  • Contact: Enqing GAO E-mail:eqgao@chem.ecnu.edu.cn

摘要:

为了获得具有刺激响应性发光功能的金属有机框架 (metal-organic frameworks, MOFs) 材料, 利用含荧光基团的烷基化试剂对含联吡啶单元的锆基MOF (Zr-bpy) 进行合成后N-烷基化修饰, 引入缺电子性吡啶基团, 同时赋予材料潜在的发光功能. 所得离子型材料 (Zr-bpy-MNap) 不发光. 但对溶剂和氨呈现选择性的荧光开启响应, 可制作成试纸用于溶剂识别和空气中氨的检测. 荧光开启响应与MOF中各种主客体相互作用和溶剂化作用有关. 材料本身不发光是由于溴离子和框架间主客体作用的淬灭效应, 而溶剂化作用或者氨与框架的主客体作用削弱或破坏了淬灭机制, 开启了来源于萘基与缺电子骨架间电荷转移跃迁的荧光.

关键词: 金属有机框架, 后合成修饰, 荧光检测,

Abstract:

In this study, the electron-deficient pyridinium group and the naphthalene fluorophore were simultaneously introduced to a bipyridyl-containing Zr(Ⅳ) metal-organic framework (MOF) by the N-alkylation post-synthetic modification. The obtained ionic MOF, Zr-bpy-MNap, is nonluminous in the pristine state but shows selective fluorescence turn-on responses to some solvents and ammonia. Test papers were prepared using the MOF for the identification of solvents and detection of ammonia in air. The fluorescence turn-on response is considered to be due to complex host-guest interactions and solvation effects. The MOF is non-fluorescent due to the quenching effects of the host-guest communications between the bromide ion and the framework. On exposure to some solvents or ammonia, the quenching mechanisms are weakened or destroyed by the solvation of bromide or host-guest interactions between ammonia and the framework, resulting in fluorescence turn-on responses. The fluorescence originates from the charge-transfer transition between the naphthyl group and the electron-deficient framework.

Key words: metal-organic frameworks, post-synthetic modification, fluorescence sensor, ammonia

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