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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Mechanism of hydrogen-bond array isomerization in tetrahydroxycalix[4]arene and tetrahydroxythiacalix[4]arene
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Mechanism of hydrogen-bond array isomerization in tetrahydroxycalix[4]arene and tetrahydroxythiacalix[4]arene

机译：四羟基杯[4]芳烃和四羟基ia杯[4]芳烃中氢键阵列异构化的机理

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摘要

Possible rearrangement mechanisms of hydrogen-bond arrays formed at the lower rim of tetrahydroxycalix[4]arene and tetrahydroxythiacalix[4]arene were studied by means of density functional theory and the resolution identity approximation modification of Moller-Plesset perturbation theory (RI-MP2). Influence of solvent to height of energy barriers was quantified by use of the conductorlike screening model (COSMO) of implicit solvent (chloroform). Generally, two types of mechanisms were investigated. The first is represented by a synchronous single-step jump of all four hydroxyl protons. Pathways of the second mechanism include the rotation of one or more hydroxyl groups around the C-Ar-O bond. Theoretical results, in agreement with recently published experimental data (Lang et al. J. Chem. Phys. 2005, 122, 044056), prefer a jump mechanism for the methylene-bridged calix[4]arene. Concerning the thiacalix[4]arene, results obtained by COSMO as well as RI-MP2 calculations show that the rotational mechanism is very competitive and it could even be more favorable.
机译：借助密度泛函理论和Moller-Plesset微扰理论（RI-MP2）的分辨率身份近似修正，研究了四羟基杯[4]芳烃和四羟基硫代杯[4]芳烃下缘形成的氢键阵列可能的重排机理。 。通过使用隐式溶剂（氯仿）的导体样筛查模型（COSMO）来量化溶剂对能垒高度的影响。通常，研究了两种类型的机制。第一个以所有四个羟基质子的同步单步跃变为代表。第二种机制的途径包括一个或多个羟基绕C-Ar-O键旋转。理论结果与最近发表的实验数据（Lang等人，J。Chem。Phys。2005，122，044056）相一致，更倾向于亚甲基桥杯[4]芳烃的跃迁机理。关于硫杂杯[4]芳烃，通过COSMO以及RI-MP2计算得出的结果表明，旋转机理非常有竞争力，甚至可能更有利。

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