LCC-CNRS, University of Toulouse, 205 route de Narbonne, 31077, Toulouse, France.
Institut de Química Computacional i Catàlisi and, Departament de Química, Universitat de Girona, c/ Maria Aurèlia Capmany 69, 17003, Girona, Catalonia, Spain.
Chemistry. 2021 Jun 25;27(36):9286-9291. doi: 10.1002/chem.202100670. Epub 2021 May 21.
After extensive studies of 1D and 2D skeletal carbo-mers based on C π-conjugating dialkynylbutatriene units (DABs: ∼C≡C-(R)C=C=C=C(R)-C≡C∼) bridging sp or sp centers in carbo-butene, carbo-xylylene or carbo-benzene derivatives, 3D versions are envisaged through carbo-barrelenes and partially reduced derivatives thereof where two or three DAB blades span a bridge between sp carbinol vertices or ether thereof. For R=Ph, stable representatives were synthesized through a pivotal [6]pericyclynedione, and extensively characterized by spectroscopic, electrochemical and crystallographic methods. Density functional theory calculations allow detailed analysis of structural and electronic features of the 7 Å high C barrel-shaped molecules, and show that they can behave as cages for ionic species. Beyond aesthetical concerns, the results could open prospects of applications in host-guest supramolecular chemistry and single molecule charge transport.
在对基于 C π共轭二炔基丁二烯单元 (DAB：∼C≡C-(R)C=C=C=C(R)-C≡C∼)桥连 sp 或 sp 中心的 1D 和 2D 骨架碳聚合物进行广泛研究之后，设想了通过碳桶烯及其部分还原衍生物的 3D 版本，其中两个或三个 DAB 叶片在 sp 仲醇顶点或醚之间跨越桥。对于 R=Ph，通过关键的 [6] 围环二酮合成了稳定的代表物，并通过光谱、电化学和晶体学方法进行了广泛的表征。密度泛函理论计算允许对 7 Å 高 C 桶形分子的结构和电子特征进行详细分析，并表明它们可以作为离子物种的笼。除了美学上的考虑之外，这些结果可能为在主客体超分子化学和单分子电荷输运中的应用开辟前景。
