Cryptophanes for Methane and Xenon Encapsulation: A Comparative Density Functional Theory Study of Binding Properties and NMR Chemical Shifts,The Journal of Physical Chemistry A

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Cryptophanes for Methane and Xenon Encapsulation: A Comparative Density Functional Theory Study of Binding Properties and NMR Chemical Shifts
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2017-12-12 00:00:00 , DOI: 10.1021/acs.jpca.7b10595
Taye B. Demissie _{1,

2} , Kenneth Ruud ₁ , Jørn H. Hansen ₂

Affiliation

The host–guest chemistry of cryptophanes is an active research area because of its applications in sensor design, targeting small molecules and atoms in environmental and medical sciences. As such, the computational prediction of binding energies and nuclear magnetic resonance (NMR) properties of different cryptophane complexes are of interest to both theoreticians and experimentalists working in host–guest based sensor development. Herein we present a study of 10 known and some newly proposed cryptophanes using density functional theory (DFT) calculations. We benchmark the description of nonbonding interactions by different DFT functionals against spin-component-scaled, second-order Møller–Plesset theory (SCS-MP2) and predict novel host molecules with enhanced affinity toward methane and Xenon, two representative systems of high interest. We demonstrate the power and limitations of the different computational methods in describing the binding and NMR properties of these established and novel host systems. The results show the importance of including dispersion corrections in the DFT functionals. The overall analysis of the dispersion corrections indicated that results obtained from pure DFT functionals should be used cautiously when conclusions are drawn for molecular systems with considerable weak interactions. Proposed analogues of cryptophane-A, where the alkoxy bridges are replaced by alkyl chains, are predicted to display enhanced affinity toward both methane and Xenon.

中文翻译：

甲烷和氙气封装的色氨酸：结合特性和NMR化学位移的比较密度泛函理论研究

色氨酸的主客体化学是一个活跃的研究领域，因为它在传感器设计中的应用是针对环境和医学领域中的小分子和原子。因此，从事基于宿主-客体传感器开发的理论家和实验家都对不同隐体复合物的结合能和核磁共振（NMR）性质的计算预测感兴趣。本文中，我们使用密度泛函理论（DFT）计算对10个已知的和一些新提出的密码子进行了研究。我们以自旋组分级的二阶Møller-Plesset理论（SCS-MP2）为基准，描述了不同DFT功能对非键相互作用的描述，并预测了对甲烷和氙气（这两个非常受关注的系统）具有更高亲和力的新型宿主分子。我们展示了不同的计算方法在描述这些已建立和新颖的宿主系统的结合和NMR特性方面的强大功能和局限性。结果表明在DFT功能中包括色散校正的重要性。色散校正的整体分析表明，当得出具有相当弱的相互作用的分子系统的结论时，应谨慎使用从纯DFT官能团获得的结果。拟议的隐烷-A的类似物（其中烷氧基桥被烷基链取代）预计对甲烷和氙都显示出增强的亲和力。结果表明在DFT功能中包括色散校正的重要性。色散校正的整体分析表明，当得出具有相当弱的相互作用的分子系统的结论时，应谨慎使用从纯DFT官能团获得的结果。拟议的隐烷-A的类似物（其中烷氧基桥被烷基链取代）预计对甲烷和氙都显示出增强的亲和力。结果表明在DFT功能中包括色散校正的重要性。色散校正的整体分析表明，当得出具有相当弱的相互作用的分子系统的结论时，应谨慎使用从纯DFT官能团获得的结果。拟议的隐烷-A的类似物（其中烷氧基桥被烷基链取代）预计对甲烷和氙都显示出增强的亲和力。

更新日期：2017-12-12

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