一种具有聚集诱导发光效应有机荧光小分子的设计合成及功能应用

doi:10.16085/j.issn.1000-6613.2022-1419

化工进展 ›› 2023, Vol. 42 ›› Issue (6): 3097-3104.DOI: 10.16085/j.issn.1000-6613.2022-1419

一种具有聚集诱导发光效应有机荧光小分子的设计合成及功能应用

张芳¹^,²^,³(), 郭鹍鹏³, 梁春平¹^,², 尤雪瑞¹^,², 张志超¹^,²

^1.山西能源学院能源化学与材料工程系，山西晋中 030604
^2.山西能源学院能源材料与低碳技术研究所，山西晋中 030604
^3.太原理工大学新材料界面科学与工程教育部重点实验室，山西太原 030024

收稿日期:2022-07-27 修回日期:2022-08-27 出版日期:2023-06-25 发布日期:2023-06-29
通讯作者: 张芳
作者简介:张芳（1989—），女，博士，讲师，研究方向为有机光电功能材料。E-mail：zhangfang@sxie.edu.cn。
基金资助:
山西省教育厅高等学校科技创新项目(2020L0733)

Design, synthesis and application research for an organic luminescent molecule with aggregation induced emission

ZHANG Fang¹^,²^,³(), GUO Kunpeng³, LIANG Chunping¹^,², YOU Xuerui¹^,², ZHANG Zhichao¹^,²

^1.Department of Energy Chemistry and Materials Engineering, Shanxi Institute of Energy, Jinzhong 030604, Shanxi, China
^2.Research Institute of Energy Materials and Low Carbon Technology, Shanxi Institute of Energy, Jinzhong 030604, Shanxi, China
^3.Ministry of Education Key Laboratory of Interface Science and Engineering in Advanced Materials, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China

Received:2022-07-27 Revised:2022-08-27 Online:2023-06-25 Published:2023-06-29
Contact: ZHANG Fang

摘要/Abstract

摘要：

有机荧光分子因其荧光性质稳定、结构易调控、成本低廉等优势吸引了众多学者的关注。为了获得具有优异性能的功能性有机荧光小分子，通过调控分子结构，利用Suzuki反应合成了一个具有聚集诱导发光效应的A-D-A型多功能有机荧光小分子APAD。通过理论计算对分子结构、能级以及电势差分布情况进行表征，表明该分子存在分子内电荷转移效应。电化学等分析手段进一步分析了其能级结构。聚集态发光性能研究表明，该分子具有典型的聚集诱导发光效应。最后，利用APAD的分子发光特性对其应用性进行了研究，发现APAD不仅可以作为有机荧光探针实现对有害物质水合肼的实时检测，并具有较高的选择性、抗干扰性，且检测限低至3.2×10^-7mol/L，还可以利用其荧光性能对温度的依赖性制备荧光温度计。

关键词: 有机荧光分子, 分子内电荷转移, 聚集诱导发光, 荧光探针, 荧光温度计

Abstract:

Great attention has been attracted by researchers due to the stable fluorescence properties, adjustable structure and low cost for organic luminescent molecules. In order to obtain functional organic luminescent molecule with excellent properties, a multifunctional organic luminescent molecule APAD with A-D-A type was synthesized by Suzuki reaction by adjusting the structure of molecule. The structure, energy level and potential difference distribution were determined by theoretical calculation, indicating the exist of intramolecular charge transfer characteristic in the molecule. The energy level was further analyzed by electrochemical analysis test. In addition, the aggregated luminescence study showed that APAD displayed typical aggregation induced emission effect. Finally, the applications for molecule APAD were studied utilizing its molecular luminescence characteristics. It was found that APAD can be used as an organic fluorescent probe to detect the harmful substance hydrazine hydrate in real-time detection with high selectivity and anti-interference, and the limit of detection is as low as 3.2×10^-7mol/L was calculated. Additionally, it was also used as a fluorescent thermometer due to its temperature dependence of fluorescent characteristics.

Key words: organic luminescent molecule, intramolecular charge transfer, aggregation induced luminescence, fluorescent probe, fluorescent thermometer

中图分类号:

O626.32

张芳, 郭鹍鹏, 梁春平, 尤雪瑞, 张志超. 一种具有聚集诱导发光效应有机荧光小分子的设计合成及功能应用[J]. 化工进展, 2023, 42(6): 3097-3104.

ZHANG Fang, GUO Kunpeng, LIANG Chunping, YOU Xuerui, ZHANG Zhichao. Design, synthesis and application research for an organic luminescent molecule with aggregation induced emission[J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3097-3104.

图/表 9

图1 APAD的理论计算相关图谱

图2 APAD的电化学测试相关图谱

表1 化合物APAD的紫外吸收及电化学性质

化合物名称	λ_onset/nm	E_g/eV	E_ox/V	E_Fe/V	E_HOMO/eV	E_LUMO/eV
APAD	475	2.61	0.79	0.25	-5.34	-2.73

图3 APAD在不同混合体系中的荧光发射光谱、紫外吸收光谱和荧光照片

图4 APAD作为荧光探针识别水合肼的荧光发射光谱、紫外吸收光谱和荧光照片

图5 APAD对水合肼的选择性和干扰性测试图谱

图6 I396nm/I483nm与水合肼滴加量之间的函数关系图

图7 APAD识别水合肼的机理

图8 APAD在25℃、0℃和-196℃ 下于365nm紫外灯激发的荧光照片

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一种具有聚集诱导发光效应有机荧光小分子的设计合成及功能应用

Design, synthesis and application research for an organic luminescent molecule with aggregation induced emission

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