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Solvent-Dependent Linear Free-Energy Relationship in a Flexible Host-Guest System.
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2020-09-11 , DOI: 10.1021/acs.joc.0c01616 Tobias J Sherbow 1 , Hazel A Fargher 1 , Michael M Haley 1 , Michael D Pluth 2 , Darren W Johnson 1
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2020-09-11 , DOI: 10.1021/acs.joc.0c01616 Tobias J Sherbow 1 , Hazel A Fargher 1 , Michael M Haley 1 , Michael D Pluth 2 , Darren W Johnson 1
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Supramolecular chemistry provides an effective strategy for the molecular recognition of diverse molecules. Significant efforts to design synthetic hosts have enabled the successful binding of many types of guests; however, less is known about how host–guest environments influence binding. Herein, we present a comprehensive study in which we measure the host–guest binding of a bis(arylethynyl phenylurea) host with a chloride guest in eight solvents spanning ET(30) values ranging from nonpolar (40.7 kcal mol–1) to polar (47.4 kcal mol–1). Polar solvents show significantly weaker binding in comparison to nonpolar solvents, and the bulk solvent polarity parameter, ET(30), shows a linear free-energy relationship with respect to the free energy of binding in the host–guest complex. These studies provide a better understanding of how host–guest binding in flexible receptors is governed by their environments and highlight the importance of host reorganization contributions in the free energy of binding. In addition, these studies highlight that preorganization may not be as important as previously thought for weak binding in which enthalpic contributions are smaller versus in polar solvents where solvent effects are magnified.
中文翻译：
灵活的主客体系统中溶剂依赖性线性自由能关系。
超分子化学为不同分子的分子识别提供了有效的策略。设计合成宿主的巨大努力使得许多类型的客人能够成功结合；然而，人们对主客体环境如何影响结合知之甚少。在此，我们提出了一项全面的研究，测量了双（芳基乙炔基苯基脲）主体与氯客体在八种溶剂中的主客体结合，涵盖E T (30) 值，范围从非极性 (40.7 kcal mol –1 ) 到极性（47.4 kcal mol –1 ）。与非极性溶剂相比，极性溶剂的结合力明显较弱，并且本体溶剂极性参数E T (30) 显示出与主客体复合物中结合自由能的线性自由能关系。这些研究提供了对柔性受体中主客体结合如何受环境控制的更好理解，并强调了宿主重组对结合自由能贡献的重要性。此外，这些研究强调，对于弱结合，预组织可能不像以前想象的那么重要，在弱结合中，与溶剂效应被放大的极性溶剂相比，其热函贡献较小。
更新日期：2020-10-02
中文翻译：
灵活的主客体系统中溶剂依赖性线性自由能关系。
超分子化学为不同分子的分子识别提供了有效的策略。设计合成宿主的巨大努力使得许多类型的客人能够成功结合；然而，人们对主客体环境如何影响结合知之甚少。在此，我们提出了一项全面的研究，测量了双（芳基乙炔基苯基脲）主体与氯客体在八种溶剂中的主客体结合，涵盖E T (30) 值，范围从非极性 (40.7 kcal mol –1 ) 到极性（47.4 kcal mol –1 ）。与非极性溶剂相比，极性溶剂的结合力明显较弱，并且本体溶剂极性参数E T (30) 显示出与主客体复合物中结合自由能的线性自由能关系。这些研究提供了对柔性受体中主客体结合如何受环境控制的更好理解，并强调了宿主重组对结合自由能贡献的重要性。此外，这些研究强调，对于弱结合，预组织可能不像以前想象的那么重要，在弱结合中，与溶剂效应被放大的极性溶剂相比，其热函贡献较小。
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