非对称联苯TADF化合物的合成与发光性质

doi:10.6023/cjoc202604042

摘要/Abstract

缺电子的3-硝基-3’-溴-6,6’-二氟联苯二腈与1当量咔唑在碱性条件下发生较为罕见的芳香亲核取代反应, 苯环上的硝基被9-咔唑基取代, 生成化合物1. 分别与2当量咔唑或二叔丁基咔唑反应, 硝基和同一个苯环上的氟原子被（二叔丁基）咔唑基取代, 生成化合物2a,b. 化合物2a与3-甲酰基苯硼酸发生钯催化的Suzuki偶联反应, 生成化合物3. 通过谱学方法、元素分析（2b）、X-射线衍射（2a和3）和密度泛函理论（DFT）方法研究了几个非对称联苯产物1-3的组成和结构, 并对该芳香亲核取代反应的机理进行了讨论. 发光性质研究表明, 化合物1-3均具有热活化延迟荧光（TADF）性质. 本文结果为非对称联苯TADF化合物的设计和合成提供了新思路.

关键词: 联苯, 芳香亲核取代, 缺电子, 热活化延迟荧光（TADF）

Under basic conditions, the electron-deficient 3-nitro-3'-bromo-6,6'-difluorodicyanobiphenyl undergoes an uncommon nucleophilic aromatic substitution (S_NAr) reaction with one equiv. of carbazole, in which the nitro group on the ring is replaced by a 9-carbazolyl, to afford compound 1, whereas in the same reactions with two equiv. of carbazole and ditertbutylcarbazole, respectively, the nitro group and the fluorine atom on the same benzene ring are substituted by 9-carbazolyl or 9-ditertbutylcarbazolyl to produce compounds 2a,b. Compound 2a undergoes a Pd-catalyzed Suzuki coupling with 3-formylphenylboronic acid to give compound 3. The structures and compositions of the products have been studied using spectroscopic methods, elemental analysis (2b), X-ray diffraction (2a and 3), as well as density functional theory (DFT) calculations, and the mechanism of the S_NAr reaction is discussed. Investigations on the emission properties show that compounds 1-3 exhibit thermally activated delayed fluorescence (TADF) properties. These results provide new ideas for the design and synthesis of unsymmetric biphenyl TADF compounds.

Key words: Biphenyl, Nucleophilic Aromatic Substitution (S_NAr), Electron-Deficient, Thermally Activated Delayed Fluorescence (TADF)

引用此文

张雪玥, 李丹, 苗金玲, 李德利, 刘广宁, 蒋绪川, 聂永. 非对称联苯TADF化合物的合成与发光性质[J]. 有机化学, doi: 10.6023/cjoc202604042.

Zhang Xueyue, Li Dan, Miao Jinling, Li Deli, Liu Guangning, Jiang Xuchuan, Nie Yong. Synthesis and Emission Properties of Unsymmetric Biphenyl TADF Compounds[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202604042.

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