Cabaleiro-Lago Enrique M, Rodríguez-Otero Jesús
Departamento de Química Física, Facultade de Ciencias, Universidade de Santiago de Compostela, Campus de Lugo, Av. Alfonso X El Sabio, s/n 27002 Lugo, Galicia, Spain.
Departamento de Química Física, Facultade de Química, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Galicia, Spain.
Phys Chem Chem Phys. 2020 Oct 7;22(38):21988-22002. doi: 10.1039/d0cp03466e.
Curvature and size effects in halogen interactions with extended aromatic species have been evaluated, employing computational methods, in dimers formed by dihalogens Cl2, Br2 and I2 with both planar (coronene and circumcoronene) and curved (corannulene, sumanene and C60) aromatic systems. The main controlling factor in these interactions is dispersion, so they become stronger as the size of the halogen grows. The nature of the interaction with the halogen changes depending on the curvature and the extension of the aromatic system. As the aromatic species becomes larger, parallel stacked structures are favoured by dispersion increases over halogen bonded ones. Parallel dimers by the concave side are also favoured as the curvature of the aromatic species increases, while the effect is the opposite by the convex side. Overall, halogen bond interactions are not favoured for large planar or curved aromatic systems; only by the convex face of the most curved structures the dispersion contribution decreases enough so as to make halogen bonded structures competitive with parallel stacked ones.
利用计算方法，对二卤分子Cl₂、Br₂和I₂与平面（蒄和外周蒄）及弯曲（碗烯、苏曼烯和C60）芳香体系形成的二聚体中卤素与扩展芳香物种之间的曲率和尺寸效应进行了评估。这些相互作用中的主要控制因素是色散作用，因此随着卤素尺寸的增大，它们会变得更强。与卤素相互作用的性质会根据芳香体系的曲率和延伸情况而改变。随着芳香物种变大，色散作用增强使得平行堆叠结构比卤键结构更受青睐。随着芳香物种曲率增加，凹面形成的平行二聚体也更受青睐，而凸面的情况则相反。总体而言，对于大的平面或弯曲芳香体系，卤键相互作用并不占优势；只有在最弯曲结构的凸面，色散作用的贡献减小到足以使卤键结构与平行堆叠结构具有竞争力。
