Baranac-Stojanović Marija
Faculty of Chemistry, University of Belgrade, Studentski trg 12-16, P.O. Box 158, Belgrade 11000, Serbia.
J Org Chem. 2020 Mar 20;85(6):4289-4297. doi: 10.1021/acs.joc.9b03472. Epub 2020 Feb 28.
Density functional theory calculations have been performed to explore the substituent effect on benzene's structure and aromaticity upon excitation to the first triplet excited state (T). Discussion is based on spin density analysis, HOMA (harmonic oscillator model of aromaticity), NICS (nucleus-independent chemical shift), ACID (anisotropy of the induced current density), and monohydrogenation free energies and shows that a large span of aromatic properties, from highly antiaromatic to strongly aromatic, could be achieved by varying the substituent. This opens up a possibility of controlling benzene's physicochemical behavior in its excited state, while molecular motion, predicted for several derivatives, could be of interest for the development of photomechanical materials.
已进行密度泛函理论计算，以探究激发至第一三重激发态（T）时取代基对苯的结构和芳香性的影响。讨论基于自旋密度分析、HOMA（芳香性的谐振子模型）、NICS（核独立化学位移）、ACID（感应电流密度的各向异性）以及单氢化自由能，结果表明，通过改变取代基，可以实现从高度反芳香性到强芳香性的大范围芳香性质。这为控制苯在激发态下的物理化学行为开辟了可能性，而预测的几种衍生物的分子运动可能对光机械材料的开发具有重要意义。
