Ochoa-Resendiz David, Batista-Romero Fidel A, Hernández-Lamoneda Ramón
Centro de Investigaciones Químicas, Universidad Autónoma del Estado de Morelos, Av. Universidad 1001, Cuernavaca 62209, Morelos, México.
J Chem Phys. 2016 Oct 28;145(16):161104. doi: 10.1063/1.4966644.
We present a theoretical characterization of the interaction of Cl and Br in the 5 and 56 clathrate cages, respectively, based on energy partitioning analysis and a study of the electronic shifts associated with transitions to the main valence bands. Our analysis clearly shows that while Br@56 does not show halogen bonding interactions in its equilibrium geometry, Cl@5 presents all the characteristics expected for halogen bonding. This is accomplished by the interaction of the usual sigma-hole with the lone pair of the closest oxygen atom involved in hydrogen bonding within the cage framework, though breaking of the hydrogen bond is not required. This possibility, which had not been considered in previous analyses, opens up a new way of looking at the interactions of dihalogens with the nearest water molecules in the cage.
我们基于能量分配分析以及对与向主要价带跃迁相关的电子位移的研究，分别给出了Cl和Br在5号和56号笼形包合物笼中的相互作用的理论表征。我们的分析清楚地表明，虽然Br@56在其平衡几何结构中未表现出卤键相互作用，但Cl@5呈现出卤键所预期的所有特征。这是通过笼框架内参与氢键形成的最接近的氧原子的孤对电子与通常的σ-空穴之间的相互作用实现的，不过并不需要破坏氢键。这种可能性在之前的分析中未被考虑到，它为研究笼中双卤分子与最近的水分子之间的相互作用开辟了一条新途径。
