π-空穴和孤对电子之间相互作用的分子静电势和“原子在分子中”分析······π/XH···π/金属···π相互作用,Journal of Computational Chemistry

当前位置： X-MOL 学术 › J. Comput. Chem. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

π-空穴和孤对电子之间相互作用的分子静电势和“原子在分子中”分析······π/XH···π/金属···π相互作用
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2017-06-30 , DOI: 10.1002/jcc.24869
Antonio Bauzá ₁ , Saikat Kumar Seth _{1,

2} , Antonio Frontera ₁

Affiliation

使用从头计算，我们分析了涉及 1,4-二硝基苯的硝基和孤对…π (lp…π)、C–H…π 或金属 (M) 的 π-空穴相互作用之间的相互作用)...π 非共价相互作用。此外，我们还使用了 1,4-亚苯基双（二氧化膦）进行比较。当 π-hole (F…N,P) 和 lp…π/C–H…π/M…π 相互作用共存于同一个超分子组装中时，发现了有趣的协同效应。这些效应是根据复合物的能量和几何特征进行理论研究的，这些特征是通过从头计算的方法 (RI-MP2/def2-TZVP) 计算的。使用巴德的“分子中的原子”理论进行电荷密度分析，以表征相互作用并根据临界点电荷密度的变化分析它们的增强或减弱。通过分子静电势计算研究静电效应对相互作用的相互影响的重要性。通过利用这些计算工具，本研究检查了这些相互作用的相互作用。© 2017 威利期刊公司。

"点击查看英文标题和摘要"

Molecular electrostatic potential and “atoms-in-molecules” analyses of the interplay between π-hole and lone pair···π/X-H···π/metal···π interactions

Using ab initio calculations, we analyze the interplay between π‐hole interactions involving the nitro group of 1,4‐dinitrobenzene and lone pair···π (lp···π), C–H···π or metal(M)···π noncovalent interactions. Moreover, we have also used 1,4‐phenylenebis(phosphine dioxide) for comparison purposes. Interesting cooperativity effects are found when π‐hole (F···N,P) and lp···π/C–H···π/M···π interactions coexist in the same supramolecular assembly. These effects are studied theoretically in terms of energetic and geometric features of the complexes, which are computed by ab initio methods (RI‐MP2/def2‐TZVP). A charge density analysis using the Bader's theory of “atoms in molecules” is carried out to characterize the interactions and to analyze their strengthening or weakening depending on the variation of charge density at critical points. The importance of electrostatic effects on the mutual influence of the interaction is studied by means of molecular electrostatic potential calculations. By taking advantage of these computational tools, the present study examines interplay of these interactions. © 2017 Wiley Periodicals, Inc.

更新日期：2017-06-30

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南