Theoretical study of macrocyclic host molecules: from supramolecular recognition to self-assembly

Supramolecular chemistry focuses on the molecular recognition and self-assembly of various building blocks through weak non-covalent interactions, including anion–π interactions, hydrogen bonding (HB) interactions, hydrophobic interactions, van der Waals (vdW) interactions, etc., which cooperatively coexist in many systems and dramatically influence the self-assembly process from the molecular level to large-scale complicated assembled structures. The multiscale modeling protocol is a powerful tool in understanding the molecular recognition and self-assembly behaviors of supramolecular systems. It is of great significance to figure out the relationship between non-covalent interactions, host–guest recognition and stimuli-responsive self-assembled structures. In this review, we summarized some representative progress in the molecular recognition and self-assembly of macrocyclic hosts, such as heteroatom-bridged heteroaromatic calixarene, cucurbit[7]uril (CB[7]) and cyclodextrin (CD), by a multiscale modeling protocol in recent years. We believe that this review on host–guest molecular recognition and self-assembly mechanisms will provide theoretical guidance for the rational design and preparation of advanced functional materials in experiments.