Sturm Ludmilla, Artigas Albert, Coquerel Yoann, Bechtold Ivan H, Durola Fabien, Bock Harald
Centre de Recherche Paul Pascal, Université de Bordeaux, 115 av. Schweitzer, 33600, Pessac, France.
Facultat de Ciències, Universitat de Girona, Campus Montilivi, Carrer de Maria Aurèlia Capmany i Farnès 69, 17003, Girona, Catalunya, Spain.
Angew Chem Int Ed Engl. 2024 Jun 3;63(23):e202403170. doi: 10.1002/anie.202403170. Epub 2024 Apr 29.
This combined experimental and theoretical study illustrates the profound consequences of non-planarity on the electronic properties of polycyclic arenes. Three isomeric [10]fibonacene tetraesters were synthesized through a robust and regiocontrolled Perkin/Mallory approach: a nearly planar [10]phenacene derivative, a moderately twisted [10]semicircle derivative, and a 3D non-planar [10]helicene derivative. The photophysical properties of the 3D [10]helicene isomer were found to be dramatically different from the comparable ones of the [10]phenacene and [10]semicircle isomers. The aromatic properties of the [10]phenacene and [10]semicircle isomers conform well with their predictive Kekulé and Clar analyses, but the [10]helicene isomer deviates from these general topological rules, which appears to be a general phenomenon for [n]fibonacenes with n≥9.
这项结合实验与理论的研究揭示了非平面性对多环芳烃电子性质的深远影响。通过一种稳健且区域可控的珀金/马洛里方法合成了三种异构的[10]菲并萘四酯：一种近乎平面的[10]菲衍生物、一种适度扭曲的[10]半圆衍生物以及一种三维非平面的[10]螺旋烯衍生物。发现三维[10]螺旋烯异构体的光物理性质与[10]菲和[10]半圆异构体的类似性质显著不同。[10]菲和[10]半圆异构体的芳香性质与其预测的凯库勒和克拉尔分析结果相符，但[10]螺旋烯异构体偏离了这些一般拓扑规则，这似乎是n≥9的[n]菲并萘的普遍现象。
