Experimental and Computational Insights into Dispersion Interactions in Self-Assembled Supramolecular Host-Guest Systems

该项目涉及超分子主体-客体系统的实验和理论研究，其中主体的结构稳定性和对客体分子的结合亲和力强烈受分散相互作用的影响。基于吖啶/吖啶酮功能化骨架的自组装配位笼将被合成并使用多种光谱工具表征，包括多维NMR技术、离子迁移质谱、X射线晶体学和等温滴定量热。模块化合成方法将允许构建不同大小和形状的分子笼，以及在结合袋中引入色散能量供体基团。这种结构在性质上是独特的，因为它们包括在生物分子系统中发现的一些复杂性，同时由于其固有的对称性或分子组装的刚性而表现出类似于低维模型的性质。最终的目标是探索这些性质，并从其他因素，如较强的非共价吸引力，空间和溶剂化效应解剖分子内和分子间的分散相互作用。理论研究将进行合成的超分子系统和/或其模型。目标有两个方面。一方面，我们希望在主-客体相互作用中区分分散力，并更好地理解与溶剂排斥效应的相互作用。另一方面，基准和完善程序，以分析相互作用能，无论分子大小。在第一个资助期内，我们已经成功地确定了一组超分子结构，具有很大的前景，比较主机稳定性，客体亲和力和溶剂效应的研究。还与优先方案的其他研究单位合作，开发和测试了分散量化的理论工具。在第二阶段，我们将扩大我们的项目范围，研究超分子主体内部的反应性以及中间体和反应产物中色散力的影响。

This project deals with the experimental and theoretical study of supramolecular host-guest systems, whereby the structural stability of the hosts and binding affinity towards guest molecules is strongly conditioned by dispersion interactions. Self-assembled coordination cages based on acridine/acridone functionalized backbones will be synthesized and characterized with a large variety of spectroscopic tools, including multidimensional NMR techniques, ion mobility mass spectrometry, X-ray crystallography and isothermal titration calorimetry.A modular synthetic approach will allow the construction of molecular cages of varying size and shape, as well as the introduction of dispersion energy donor groups in the binding pocket(s). Such structures are unique in character, as they include some of the complexity found in biomolecular systems, while exhibiting properties akin to low-dimensional models, either due to their inherent symmetry or the rigidity of the molecular assembly. The ultimate goal is to explore such properties and to dissect intra- and intermolecular dispersion interactions from other factors such as stronger non-covalent attractions, steric and solvation effects.Theoretical studies will be carried out on the synthesised supramolecular systems and/or models thereof. The objectives are two-fold. On one hand, we wish to distinguish dispersion forces in host-guest interactions and better understand the interplay with solvent exclusions effects. On the other hand, to benchmark and refine procedures to analyse interaction energies, irrespective of molecular size. In the first funding period, we have successfully identified a group of supramolecular structures with great promise for the study of comparative host stability, guest affinity and solvent effects. Theoretical tools for the quantification of dispersion have also been developed and tested in cooperation with other research units in the Priority Programme. In the second phase, we will expand the scope of our project to the study of reactivity inside supramolecular hosts and the impact of dispersion forces in intermediates and reaction products.