The boron dipyrromethene (BODIPY) triads consisting of two triphenylamine units as electron donor (D) and BODIPY core as electron acceptor (A; B3, and B4) have been synthesized using facile palladium cross-coupling reactions to broaden the absorption of the BODIPY dyes. All dyes and intermediates were characterized by 1H NMR, 11B NMR, 13C NMR, and 19F NMR spectroscopies, UV–Vis spectroscopy, fluorescence spectroscopy, cyclic voltammetry, and time-dependent density functional theory calculations. It was found that an increase in conjugation to the BODIPY core systematically extended the absorption and emission wavelength maxima. As a consequence, B4 containing the D–π–A–π–D structure, exhibited the longest absorption and emission maxima at 597 and 700 nm, respectively, with 1.8 eV in optical bandgap. The 96 nm red-shifted absorption of B4 as compared to the unsubstituted BODIPY (B1) indicated the effective electronic communication between triphenylamine and BODIPY. This suggested that the proper alignment of triphenylamine and BODIPY triad could lead to broader absorption and suitable low energy bandgap. Furthermore, the molecular modeling has been employed to analyze the electronic and optical properties of the dyes. We found that the optical, electrochemical, and theoretical bandgaps of all dyes were in good agreement.

中文翻译：

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含有三苯胺的 BODIPY 的合成、光学和电化学性质以及理论计算

由两个三苯胺单元作为电子供体 (D) 和 BODIPY 核作为电子受体 (A; B3 和 B4) 组成的硼二吡咯甲烯 (BODIPY) 三元组已使用简便的钯交叉偶联反应合成，以拓宽 BODIPY 染料的吸收. 所有染料和中间体均通过 1H NMR、11B NMR、13C NMR 和 19F NMR 光谱、UV-Vis 光谱、荧光光谱、循环伏安法和时间相关密度泛函理论计算进行表征。发现与 BODIPY 核心共轭的增加系统地扩展了吸收和发射波长最大值。因此，含有 D-π-A-π-D 结构的 B4 分别在 597 和 700 nm 处表现出最长的吸收和发射最大值，光学带隙为 1.8 eV。与未取代的 BODIPY (B1) 相比，B4 的 96 nm 红移吸收表明三苯胺和 BODIPY 之间存在有效的电子通讯。这表明三苯胺和 BODIPY 三元组的正确排列可以导致更宽的吸收和合适的低能带隙。此外，分子建模已被用于分析染料的电子和光学特性。我们发现所有染料的光学、电化学和理论带隙都非常吻合。分子模型已被用于分析染料的电子和光学特性。我们发现所有染料的光学、电化学和理论带隙都非常吻合。分子模型已被用于分析染料的电子和光学特性。我们发现所有染料的光学、电化学和理论带隙都非常吻合。