A photoredox‐catalyst‐ and template‐free sunlight‐induced molecular dimerization of a vinylpyridine‐functionalized tetraarylaminoborane (TAAB) has been accomplished for the first time. The reaction is quantitative, highly regioselective, and thermally irreversible. The presence of the propeller‐shaped TAAB framework allows selective photodimerization of one of the two vinyl pyridine units. Monomer 1 and photodimer 2 exhibit distinct photophysical properties with delayed fluorescence (DF) both in solution and the solid state, which was confirmed by steady‐state and time‐resolved luminescence studies. Quantum mechanical calculations were performed to support the experimental observations. Our new approach using [2+2] cycloaddition chemistry paves the way for the development of highly sought‐after deep‐blue DF materials.

中文翻译：

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乙烯基吡啶官能化的四芳基氨基硼烷的无催化剂和无模板超快可见光引发的二聚反应：引人入胜的深蓝色延迟荧光

首次完成了光催化还原和无模板的乙烯基吡啶官能化的四芳基氨基硼烷（TAAB）的分子二聚化反应。该反应是定量的，高度区域选择性的并且是热不可逆的。螺旋桨形TAAB骨架的存在允许两个乙烯基吡啶单元之一的选择性光二聚化。单体1和光电二聚体2在溶液和固态中均表现出独特的光物理特性，并具有延迟的荧光（DF），这已通过稳态和时间分辨的发光研究得到了证实。进行量子力学计算以支持实验观察。我们使用[2 + 2]环加成化学的新方法为开发广受欢迎的深蓝色DF材料铺平了道路。