Orbital Nature of Carboionic Monoradicals Made from Diradicals
Orbital Nature of Carboionic Monoradicals Made from Diradicals
复制标题
由双自由基制成的碳离子单自由基的轨道性质
DOI：
10.1002/chem.202300388
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Haley, Michael M.
中科院分区：
文献类型：
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作者：
Valdivia, Abel Cardenas;Dai, Yasi;Rambaldi, Filippo;Barker, Joshua E.;Dressler, Justin J.;Zhou, Zheng;Zhu, Yikun;Wei, Zheng;Petrukhina, Marina A.;Haley, Michael M.
本文研究了由中性双自由基出发得到的一系列单自由基、阴离子和阳离子的电子、光学和固态性质。基于-引达省和茚并省的双自由基，具有稠合的苯并噻吩和不同的取向，在中性状态下具有不同程度的双自由基特征，这与自由基氧化还原形式的性质有关。在分子轨道和价键理论的框架下，对多甲川单价自由基的光学性质进行了分析。进行了电子紫外-维斯-近红外吸收、X射线固态衍射和量子化学计算。不同的正/负电荷物种的研究，都驻留在相同的骨架π共轭骨架，是罕见的有机分子。双重稳定化的关键因素是起始双自由基特征的存在，其使得能够以用于双极电荷传输的确定小的重组能量不明显地容纳赝空穴和赝电子缺陷。
The electronic, optical, and solid state properties of a series of monoradicals, anions and cations obtained from starting neutral diradicals have been studied. Diradicals based ons‐indacene and indenoacenes, with benzothiophenes fused and in different orientations, feature a varying degree of diradical character in the neutral state, which is here related with the properties of the radical redox forms. The analysis of their optical features in the polymethine monoradicals has been carried out in the framework of the molecular orbital and valence bond theories. Electronic UV‐Vis‐NIR absorption, X‐ray solid‐state diffraction and quantum chemical calculations have been carried out. Studies of the different positive‐/negative‐charged species, both residing in the same skeletalπ‐conjugated backbone, are rare for organic molecules. The key factor for the dual stabilization is the presence of the starting diradical character that enables to indistinctively accommodate a pseudo‐hole and a pseudo‐electron defect with certainly small reorganization energies for ambipolar charge transport.