Department of Physical Chemistry, University of Málaga, Andalucia-Tech Campus de Teatinos s/n, 29071, Málaga, Spain.
Dipartimento di Chimica 'Giacomo Ciamician', Università di Bologna, Via F. Selmi, 2, 40126, Bologna, Italy) and INSTM, UdR, Bologna (Italy.
Chemistry. 2023 May 11;29(27):e202300388. doi: 10.1002/chem.202300388. Epub 2023 Mar 23.
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 on s-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 skeletal π-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.
已经研究了一系列单自由基、阴离子和阳离子的电子、光学和固态特性，这些单自由基、阴离子和阳离子是从起始中性双自由基获得的。基于 s-茚并芴和茚并并苯的双自由基，与苯并噻吩融合且具有不同的取向，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特性有关。在聚甲川单自由基中，对其光学特性进行了分子轨道和价键理论的分析。进行了电子紫外可见近红外吸收、X 射线固态衍射和量子化学计算的研究。对于有机分子来说，研究同一骨架π共轭主链中不同的正/负电荷物种是罕见的。双稳定的关键因素是存在起始的双自由基特性，这使得能够以一定的小重组能来容纳伪空穴和伪电子缺陷，从而实现双极性电荷输运。
