From weak to strong interactions: structural and electron topology analysis of the continuum from the supramolecular chalcogen bonding to covalent bonds
From weak to strong interactions: structural and electron topology analysis of the continuum from the supramolecular chalcogen bonding to covalent bonds
复制标题
从弱相互作用到强相互作用：从超分子硫族键合到共价键的连续体的结构和电子拓扑分析
DOI：
10.1039/d1cp05441d
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发表时间：
2022
影响因子：
3.3
通讯作者：
Rosokha, Sergiy V.
中科院分区：
文献类型：
--
作者：
Miller, Daniel K.;Chernyshov, Ivan Yu.;Torubaev, Yury V.;Rosokha, Sergiy V.
通过查阅剑桥结构数据库中的含硒和含碲结构，并利用分子原子量子理论（Quantum Theory of Atoms in Molecules， QTAIM）对其进行计算分析，探讨了共价键和超分子键之间的关系，以及不同相互作用的赋值准则。这项联合研究揭示了原子间Se⋯Br和Te⋯I距离，dCh⋯X的连续体，从这些原子的范德华半径（rCh + rX）的总和到它们的共价键长度的一系列关联。键临界点处的电子密度ρ(r)从非共价相互作用的约0.01 a.u.逐渐增加到共价键的约0.1 a.u.。当根据归一化原子间距离绘制时，对数ρ(r)值落在同一线性趋势线上，RXY = dCh⋯X/(rCh + rX)。在RXY≈0.80时，观察到bcp的能量密度H(r)从正向负的转变（与基本非共价相互作用转变为部分共价相互作用有关）。与RXY成键特性的同步变化（类似于先前在卤素键系统中发现的情况）表明，标准化原子间分离是决定这些键性质的关键因素。Te， I和Se， Br键长度的不间断连续性和bcp的特征表明，涉及硫原子的键的限制类型之间以及共价键和超分子键之间存在内在联系。
The relationship between covalent and supramolecular bonding, and the criteria of the assignments of different interactions were explored via the review of selenium and tellurium containing structures in the Cambridge Structural Database and their computational analysis using Quantum Theory of Atoms in Molecules (QTAIM). This combined study revealed continuums of the interatomic Se⋯Br and Te⋯I distances, dCh⋯X, in the series of associations from the sums of the van der Waals radii of these atoms (rCh + rX) to their covalent bond lengths. The electron densities, ρ(r), at Bond Critical Points (BCPs) along the chalcogen bond paths increased gradually from about 0.01 a.u. common for the non-covalent interactions to about 0.1 a.u. typical for the covalent bonds. The log ρ(r) values fell on the same linear trend line when plotted against normalized interatomic distances, RXY = dCh⋯X/(rCh + rX). The transition from the positive to negative values of the energy densities, H(r), at the BCPs (related to a changeover of essentially non-covalent into partially covalent interactions) were observed at RXY ≈ 0.80. Synchronous changes of bonding characteristics with RXY (similar to that found earlier in the halogen-bonded systems) designated normalized interatomic separation as a critical factor determining the nature of these bondings. The uninterrupted continuums of Te⋯I and Se⋯Br bond lengths and BCPs’ characteristics signified an intrinsic link between limiting types of bonding involving chalcogen atoms and between covalent and supramolecular bonding in general.