Saha Ranajit, Chattaraj Pratim K
Department of Chemistry and Center for Theoretical Studies, Indian Institute of Technology Kharagpur, Kharagpur 721302, India.
Department of Chemistry, Indian Institute of Technology Bombay, Mumbai 400076, India.
ACS Omega. 2018 Dec 13;3(12):17199-17211. doi: 10.1021/acsomega.8b03006. eCollection 2018 Dec 31.
A density functional theory-based computation has been carried out to reveal the geometrical and electronic structures of MgEP (), where EP is an extended (3.1.3.1) porphyrinoid system. EP is a 22 π electronic system and is aromatic in nature. Here, we have studied the thermodynamic and kinetic stabilities of EP-supported Mg ion. The nature of bonding has been studied using natural bond orbital and atoms in molecule schemes. The presence of a covalent Mg(I)-Mg(I) σ-bond in MgEP is confirmed. The occurrence of a non-nuclear attractor (NNA) with large electron population, negative Laplacian of electron density at NNA, and presence of an electron localization function basin along with large nonlinear optical properties prompt us to classify MgEP as the first porphyrinoid-based organic electride. Further five small molecules, viz., dihydrogen (H), carbon dioxide (CO), nitrous oxide (NO), methane (CH), and benzene (CH), are found to be activated by the electron density between the two Mg atoms in MgEP.
已进行基于密度泛函理论的计算以揭示MgEP（其中EP是一种扩展的(3.1.3.1)类卟啉体系）的几何结构和电子结构。EP是一个22π电子体系，本质上具有芳香性。在此，我们研究了EP负载的Mg离子的热力学和动力学稳定性。已使用自然键轨道和分子中的原子方法研究了键合性质。证实了MgEP中存在共价Mg(I)-Mg(I)σ键。具有大量电子占据的非核吸引子（NNA）的出现、NNA处电子密度的负拉普拉斯以及电子定域函数盆地的存在以及大的非线性光学性质促使我们将MgEP归类为首个基于类卟啉的有机电子化物。此外，发现五个小分子，即氢气（H₂）、二氧化碳（CO₂）、一氧化二氮（N₂O）、甲烷（CH₄）和苯（C₆H₆）被MgEP中两个Mg原子之间的电子密度激活。
