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

本项目致力于超分子主客体体系的实验和理论研究，其中主体的结构稳定性和与客体分子的结合亲和力强烈地受到分散相互作用的制约。我们将合成并利用多种光谱手段进行表征，包括多维核磁共振技术、离子迁移率质谱仪、X射线结晶学和等温滴定量热法。模块化的合成方法将允许构建不同大小和形状的分子笼子，并在结合袋中引入分散的能量供体基团(S)。这种结构在性质上是独一无二的，因为它们包括了生物分子系统中的一些复杂性，同时表现出类似于低维模型的性质，这要么是由于它们固有的对称性，要么是由于分子组装的刚性。最终的目标是探索这些性质，并从更强的非共价吸引、空间和溶剂化效应等其他因素中剖析分子内和分子间的分散相互作用。将对合成的超分子体系和/或其模型进行理论研究。目标有两个。一方面，我们希望区分主客体相互作用中的色散力，并更好地了解与溶剂排除效应的相互作用。另一方面，以基准和改进程序来分析相互作用能量，而不考虑分子大小。在第一个资助期，我们成功地鉴定了一组超分子结构，这些超分子结构在比较宿主稳定性、客体亲和力和溶剂效应的研究中具有很大的前景。还与优先方案中的其他研究单位合作，开发和测试了量化分散程度的理论工具。在第二阶段，我们将把我们的项目范围扩大到研究超分子主体内部的反应性，以及中间体和反应产物中分散力的影响。

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.