Lewis‐Pairing‐Induced Electrochemiluminescence Enhancement from Electron Donor‐Acceptor Diads Decorated with Tris(pentafluorophenyl)borane as an Electrochemical Protector
Lewis‐Pairing‐Induced Electrochemiluminescence Enhancement from Electron Donor‐Acceptor Diads Decorated with Tris(pentafluorophenyl)borane as an Electrochemical Protector
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用三（五氟苯基）硼烷作为电化学保护剂修饰的电子供体-受体二元组的路易斯配对诱导的电化学发光增强
DOI：
10.1002/anie.202301109
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Abe Masaaki
中科院分区：
文献类型：
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作者：
Ikeda Takashi;Tahara Keishiro;Ishimatsu Ryoichi;Ono Toshikazu;Cui Luxia;Maeda Momoka;Ozawa Yoshiki;Abe Masaaki
本研究报道了用 B(C6F5)3 对有机供体-受体二元组进行有效的外围装饰，以稳定电产生的自由基离子。通过采用常见的p型有机半导体苯并噻吩并噻吩（BTBT）作为供体，四配位硼配合物表现出改善的溶液电化学发光（ECL）强度，与母体二元组相比增加了156倍。前所未有的路易斯配对诱导的 ECL 增强归因于 B(C6F5)3 的多重作用：1) 重新分布前沿轨道，2) 促进电化学激发，3) 限制分子运动。此外，B(C6F5)3 将 BTBT 的分子排列从传统的 2D 人字形转变为 1D π 堆叠。这种坚固、高度有序的柱状纳米结构允许通过 BTBT 的电子耦合途径进行电化学掺杂的结晶膜 ECL 发生红移。我们的方法将促进复杂的无金属 ECL 系统的开发。
This study reports an effective peripheral decoration of organic donor‐acceptor diads with B(C6F5)3for stabilizing electrogenerated radical ions. By employing a common p‐type organic semiconductor benzothienobenzothiophene (BTBT) as the donor, tetracoordinate boron complexes showed improved solution electrochemiluminescence (ECL) intensity, reaching a 156‐fold increase compared to that of the parent diad. The unprecedented Lewis‐pairing‐induced ECL enhancement is attributed to the multiple roles of B(C6F5)3: 1) redistributing frontier orbitals, 2) facilitating electrochemical excitation, and 3) restricting molecular motions. Furthermore, B(C6F5)3converted the molecular arrangement of BTBT from conventional 2D herringbones into 1D π‐stacks. This robust, highly ordered columnar nanostructure allowed red‐shifting of the crystalline film ECL with electrochemical doping through the electronic coupling pathways of BTBT. Our approach will facilitate the development of elaborate metal‐free ECL systems.