热辅助延迟荧光共轭高分子实现多种模式的电化学发光

引用本文: 孔怡, 曾梓晖, 黄萍, 罗野林, 张保华, 陈丽娟, 张玉微, 韩冬雪, 程延祥, 牛利. 热辅助延迟荧光共轭高分子实现多种模式的电化学发光[J]. 分析化学, 2021, 49(6): 1015-1024. doi: 10.19756/j.issn.0253-3820.210424 shu

Citation: KONG Yi, ZENG Zi-Hui, HUANG Ping, LUO Ye-Lin, ZHANG Bao-Hua, CHEN Li-Juan, ZHANG Yu-Wei, HAN Dong-Xue, CHENG Yan-Xiang, NIU Li. Multiple Modes of Electrochemiluminescence Using Thermally Activated Delayed Fluorescent Polymer[J]. Chinese Journal of Analytical Chemistry, 2021, 49(6): 1015-1024. doi: 10.19756/j.issn.0253-3820.210424 shu

热辅助延迟荧光共轭高分子实现多种模式的电化学发光

孔怡 ^1, ,
曾梓晖 ^1, ,
黄萍 ^1, ,
罗野林 ^1, ,
张保华 ^{1,
,} ,
陈丽娟 ^1, ,
张玉微 ^1, ,
韩冬雪 ^{1,
,} ,
程延祥 ^2, ,
牛利 ^{1,
,}

1.
广州大学化学化工学院, 分析科学技术研究中心, 广州 510006;
2.
中国科学院长春应用化学研究所, 高分子物理与化学国家重点实验室, 长春 130022

通讯作者: 张保华,E-mail:ccbhzhang@gzhu.edu.cn; 韩冬雪,E-mail:dxhan@gzhu.edu.cn; 牛利,E-mail:lniu@gzhu.edu.cn

基金项目:
广东省自然科学基金项目（Nos.2019B010933001，2021A1515010510）和国家自然科学基金项目（No.51773195）资助。

摘要: 热辅助延迟荧光（Thermally activated delayed fluorescent，TADF）发光材料是新型的纯有机电化学发光（Electrochemiluminescence，ECL）材料，具有合成简便、不含贵金属、生物相容性好、颜色易调节、发光效率高等优势。与传统的荧光有机材料只能利用单线态发光相比，TADF发光材料基于热活化性质，能发生快速、高效的反向系间窜越，使得三线态激子向单线态激子发生有效上转换，实现暗态三线态激子的辐射复合利用。TADF型ECL发光材料能够克服自旋禁阻效应，有望实现近100%的ECL发光效率。但目前尚未有实现全部典型模式下的ECL行为的TADF型ECL的体系材料。本研究基于一种高效的TADF共轭高分子材料，实现了全部典型的ECL发光模式（包括湮灭式、阶跃式、阳极共反应剂式和阴极共反应剂式），特别是通过优化TADF高分子电极制备条件和共反应剂用量，获得了有效的阴极共反应剂式ECL。对此TADF高分子的光物理特征、电化学和电化学发光性质进行了系统研究，与传统荧光高分子的ECL效率进行对比，证明了TADF高分子在电极修饰型ECL研究中，实现高ECL发光效率的潜在优势。

关键词:

English

Multiple Modes of Electrochemiluminescence Using Thermally Activated Delayed Fluorescent Polymer

1.
Centre for Advanced Analytical Science, c/o School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, China;
2.
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China

Corresponding author: ZHANG Bao-Hua, ; HAN Dong-Xue, ; NIU Li,

Received Date: 09 April 2021
Revised Date: 24 April 2021
Fund Project:
Supported by the Natural Science Foundation of Guangdong Province, China (Nos.2019B010933001, 2021A1515010510) and the National Natural Science Foundation of China (No.51773195).

Abstract: Thermally activated delayed fluorescent (TADF) emitter is becoming one promising candidate as efficient electrochemiluminescence (ECL) chromophore. Compared to other types of purely organic ECL emitter, TADF emitters possess efficient triplet-to-singlet up-conversion capability via thermal activation, which can be more efficient for ECL emission since the dominant triplets (-75% in total under electrochemical excitation) can be harvested in this case. Previously, restricted by electrochemical stability of TADF emitters, various typical ECL modes, especially for reductive-oxidation co-reactant ECL mode, were not fully realized for TADF-type ECL system. In this work, one backbone-donor/pendant-acceptor type TADF conjugated polymer (named as PFSOTT5) was used to evaluate its potential in ECL topic. Impressively, such polymer displayed good electrochemical behaviors, which rendered the successful realization of all typical ECL mode including annihilation ECL, oxidative-reduction co-reactant ECL, reductive-oxidation co-reactant ECL with good stability. Systematic photophysics, electrochemical and ECL characterization and discussion were performed for PFSOTT5 in this work. Especially, for reductive-oxidation ECL using BPO as co-reactant, PFSOTT5-based ECL displayed stable and efficient ECL emission. The ECL efficiency of PFSOTT5-based ECL was even 5.79 times as compared to the typical fluorescent polymer counterpart. Accordingly, it is anticipated that such TADF polymer ECL has the application potentials in different ECL modes.

Key words:

Electrochemiluminescence
/ Thermally activated delayed fluorescence
/ Co-reactant electrochemiluminescence
/ Electrochemistry
/ Triplet excitons

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沈阳化工大学材料科学与工程学院沈阳 110142

热辅助延迟荧光共轭高分子实现多种模式的电化学发光

通讯作者: 张保华,E-mail:ccbhzhang@gzhu.edu.cn; 韩冬雪,E-mail:dxhan@gzhu.edu.cn; 牛利,E-mail:lniu@gzhu.edu.cn

English

Multiple Modes of Electrochemiluminescence Using Thermally Activated Delayed Fluorescent Polymer

Corresponding author: ZHANG Bao-Hua, ; HAN Dong-Xue, ; NIU Li,

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

热辅助延迟荧光共轭高分子实现多种模式的电化学发光

通讯作者: 张保华,E-mail:ccbhzhang@gzhu.edu.cn; 韩冬雪,E-mail:dxhan@gzhu.edu.cn; 牛利,E-mail:lniu@gzhu.edu.cn

English

Multiple Modes of Electrochemiluminescence Using Thermally Activated Delayed Fluorescent Polymer

Corresponding author: ZHANG Bao-Hua, ; HAN Dong-Xue, ; NIU Li,

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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