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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Conformational analysis of 18-azacrown-6 and its bonding with late first transition series divalent metals: Insight from DFT combined with NPA and QTAIM analyses
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Conformational analysis of 18-azacrown-6 and its bonding with late first transition series divalent metals: Insight from DFT combined with NPA and QTAIM analyses

机译：18-azacrown-6的构象分析及其与较晚的第一过渡系列二价金属的键合：DFT与NPA和QTAIM分析相结合的见解

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摘要

Density functional theory calculations, together with quantum theory of atoms in molecules (QTAIM) analyses, have been performed to investigate 18-azacrown-6 complexes of the high-spin late first transition series divalent metal ions in the gas phase and, in some cases, in aqueous solution simulated by a polarizable continuum model. Six intramolecular H-H bonding interactions in the meso-complexes are found to arise from folding of the ligand upon its electrostatic interaction with the metal ions, which are largely absent in the lowest-energy C_(2h) conformer of the free ligand. The ligand-to-metal charge transfer obtained from QTAIM analysis, among other things, is found to be an important factor that controls the stability of these complexes. The inter-relationship between the ligand preorganization energy, the zero-point corrected formation energy of the metal complexes, and the H-H bonding pair distances, as well as the dependence of the electron density and the total energy density at the H-H bond critical points on the H-H bonding pair distances, provides a physical basis for understanding and explaining the stabilizing nature of these closed-shell interactions, which are often viewed as steric clashes that lead to complex destabilization.
机译：已经进行了密度泛函理论计算以及分子中原子的量子理论（QTAIM）分析，以研究气相中高自旋晚期第一过渡系列二价金属离子的18-azacrown-6配合物，在某些情况下在可极化连续体模型模拟的水溶液中。发现配位体与金属离子发生静电相互作用时，配体折叠会产生中观复合物中的六个分子内H-H键相互作用，而游离离子的最低能级C_（2h）构象异构体中大部分不存在这种折叠。从QTAIM分析获得的配体到金属的电荷转移是控制这些配合物稳定性的重要因素。配体预组织能，金属配合物的零点校正形成能与HH键对距离之间的相互关系，以及HH键临界点上电子密度和总能量密度的依赖性HH键对距离为理解和解释这些闭壳相互作用的稳定性质提供了物理基础，这些闭壳相互作用通常被视为导致复杂不稳定的空间碰撞。

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