Tuning the Properties of Azadipyrromethene-Based Near-Infrared Dyes Using Intramolecular BO Chelation and Peripheral Substitutions
Tuning the Properties of Azadipyrromethene-Based Near-Infrared Dyes Using Intramolecular BO Chelation and Peripheral Substitutions
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DOI：
10.1021/acs.inorgchem.1c01597
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发表时间：
2021-08-12
影响因子：
4.6
通讯作者：
Sauve, Genevieve
中科院分区：
文献类型：
--
作者：
Jimenez, Jayvic C.;Zhou, Zehao;Sauve, Genevieve
四苯基氮杂二吡咯亚甲基（ADP）由于其合成简单和优异的光学和电子性质，是一种有吸引力的近红外（NIR）染料。典型的BF 2和较少探索的分子内BO配位使分子平坦化，使它们成为有机电子应用的有希望的p-共轭材料。然而，它们的使用主要限于真空沉积装置。为了进一步改善这些性质，我们合成并表征了一系列ADP配合物，并用密度泛函理论计算进一步解释了这些性质。己氧基增溶基团增加了络合物在有机溶剂中的溶解度，并使溶液能够成膜。在吡咯位置的苯乙炔基延长p共轭，红移吸收和发射峰，并增加电离电位（IP）和电子亲和势。当比较具有己氧基和苯乙炔基取代的络合物的性质时，BO络合物比相应的BF 2络合物更平坦并且具有更小的IP，这是因为近端苯基上的电子密度增加。BO配合物具有不寻常的性质组合：溶液最大值为781 nm，发射波长为805 nm，斯托克斯位移小，量子产率为6%。它形成具有1.22 eV的低光学带隙的透明膜。这种新的复合物是透明太阳能电池和近红外光电探测器的一个有前途的候选者。
Tetraphenylazadipyrromethenes (ADPs) are attractive near-infrared (NIR) dyes because of their simple synthesis and exceptional optical and electronic properties. The typical BF2 and less explored intramolecular BO coordination planarize the molecule, making them promising p-conjugated materials for organic electronic applications. However, their use has been mostly limited to vacuumdeposited devices. To improve the properties, we synthesized and characterized a series of ADP complexes and used density functional theory calculations to further explain the properties. Hexyloxy solubilizing groups increase the complexes' solubility in organic solvents and enable film formation from solution. Phenylethynyls at the pyrrolic positions extend p conjugation, red-shift absorption and emission peaks, and increase the ionization potential (IP) and electron affinity. When the properties of complexes with hexyloxy and phenyethynyl substitutions are compared, the BO complex is more planar and has a smaller IP than the corresponding BF2 complex because of increased electron density on the proximal phenyls. The BO complex has an unusual combination of properties: a solution.max of 781 nm, emission at 805 nm, a small Stokes shift, and a quantum yield of 6%. It forms transparent films with a low optical gap of 1.22 eV. This new complex is a promising candidate for transparent solar cells and NIR photodetectors.