Yu Donghai, Stuyver Thijs, Rong Chunying, Alonso Mercedes, Lu Tian, De Proft Frank, Geerlings Paul, Liu Shubin
Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China), College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, 410081, China.
Phys Chem Chem Phys. 2019 Aug 21;21(33):18195-18210. doi: 10.1039/c9cp01623f.
In this work, we report a systematic study on the global and local aromaticity of acenes using a series of model structures from 2-acene to 11-acene. A recently developed ansatz, an information-theoretic approach coached into density functional reactivity theory has been employed, which essentially provides different density functionals characterizing the molecular electron density distribution. Based on the correlation analysis of six conventional aromaticity indices with eight information-theoretic quantities, we examined the aromaticity of acenes from both global and local perspectives. From the global aromaticity viewpoint, our results suggest that different descriptors based on various physicochemical properties are intrinsically dependent. A novel laminated feature ruling local aromaticity of acenes has been unveiled, from which we found that the distance from the terminal rings plays the critical role. Based on the shape of the correlation plots between the conventional aromaticity indices and information-theoretic quantities, the latter could be separated into three subgroups. The seemingly contradictory results from global and local aromaticity perspectives not only present us the uniqueness of the acene systems but all demonstrate the effectiveness of the information-theoretic approach from density functional reactivity theory. Besides strengthening the validity of a series of new aromaticity descriptors, our results should lead to more clear insights into the chemical significance of the information-theoretic quantities.
在这项工作中，我们使用从2-并苯到11-并苯的一系列模型结构，对并苯的全局和局部芳香性进行了系统研究。我们采用了一种最近开发的方法，即将信息论方法融入密度泛函反应理论，该方法本质上提供了表征分子电子密度分布的不同密度泛函。基于六个传统芳香性指标与八个信息论量的相关性分析，我们从全局和局部角度研究了并苯的芳香性。从全局芳香性的角度来看，我们的结果表明，基于各种物理化学性质的不同描述符本质上是相互依赖的。揭示了一种决定并苯局部芳香性的新型层状特征，从中我们发现末端环的距离起着关键作用。根据传统芳香性指标与信息论量之间相关图的形状，后者可分为三个子组。从全局和局部芳香性角度看似矛盾的结果，不仅向我们展示了并苯体系的独特性，而且都证明了来自密度泛函反应理论的信息论方法的有效性。除了加强一系列新的芳香性描述符的有效性外，我们的结果应该能让人们更清楚地了解信息论量的化学意义。
