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

本项目涉及超分子宿主-客体系统的实验和理论研究，其中宿主的结构稳定性和对客体分子的结合亲和力受到色散相互作用的强烈制约。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进行表征，包括多维核磁共振技术、离子迁移率质谱、x射线晶体学和等温滴定量热法。模块化合成方法将允许构建不同大小和形状的分子笼，以及在结合口袋中引入色散能量供体基团。这种结构在性质上是独一无二的，因为它们包含了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特性。最终目标是探索这些性质，并从其他因素（如更强的非共价吸引力、空间和溶剂化效应）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/或模型进行理论研究。目标是双重的。一方面，我们希望区分主客体相互作用中的分散力，并更好地理解溶剂排斥效应的相互作用。另一方面，在不考虑分子大小的情况下，对分析相互作用能的程序进行基准测试和改进。在第一个资助期，我们已经成功地确定了一组具有比较宿主稳定性，客体亲和力和溶剂效应研究前景的超分子结构。还与优先方案的其他研究单位合作，开发和试验了量化扩散的理论工具。在第二阶段，我们将扩大我们项目的范围，研究超分子宿主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.