Investigations into the nature of halogen bonding including symmetry adapted perturbation theory analyses
Investigations into the nature of halogen bonding including symmetry adapted perturbation theory analyses
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DOI：
10.1021/ct700216w
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发表时间：
2008-02-01
影响因子：
5.5
通讯作者：
Hobza, Pavel
中科院分区：
文献类型：
--
作者：
Riley, Kevin E.;Hobza, Pavel
近年来，人们认识到卤素键由于其独特的性质，在开发新的药物化合物和材料方面具有巨大的潜力。在本研究中，我们通过对卤甲烷-甲醛配合物以及氟取代的FnH3-nCX中心点中心点中心点OCH2二聚体进行从头计算来研究卤素成键现象。卤素(X)是氯、溴和碘。耦合团簇（CCSD(T)/ augg -cc- pvtz）计算表明，这类相互作用的结合能介于- 1.05 kcal/mol （H3CCl中心点中心点中心点OCH2）和-3.72 kcal/mol （F3Cl中心点中心点中心点OCH2）之间。本研究中最重要的发现之一是，根据对称自适应摄动理论（SAPT）分析，卤素键在很大程度上依赖于静电和色散型相互作用。当参与卤素键的卤素原子变大时，这种相互作用的相互作用强度也变大，有趣的是，这种相互作用的静电性更强（而色散性更弱）。当（电负性很强的）氟取代到卤甲烷分子上时，卤素键的相互作用也变得更强、更静电。
In recent years it has been recognized that, because of their unique properties, halogen bonds have tremendous potential in the development of new pharmaceutical compounds and materials. In this study we investigate the phenomenon of halogen bonding by carrying out ab initio calculations on the halomethane-formaldehyde complexes as well as the fluorine substituted FnH3-nCX center dot center dot center dot OCH2 dimers, where the halogen bonding. halogens (X) are chlorine, bromine, and iodine. Coupled cluster (CCSD(T)/aug-cc-pVTZ) calculations indicate that the binding energies for these type of interactions lie in the range between - 1.05 kcal/mol (H3CCl center dot center dot center dot OCH2) and -3.72 kcal/mol (F3Cl center dot center dot center dot OCH2). One of the most important findings in this study is that, according to symmetry adapted perturbation theory (SAPT) analyses, halogen bonds are largely dependent on both electrostatic and dispersion type interactions. As the halogen atom involved in halogen bonding becomes larger the interaction strength for this type of interaction also gets larger and, interestingly, more electrostatic (and less dispersive) in character. Halogen bonding interactions also become stronger and more electrostatic upon substitution of (the very electronegative) fluorines onto the halomethane molecule.