Dynamic macromolecular material design: the versatility of cucurbituril over cyclodextrin in host–guest chemistry

Abstract

The keto–enol tautomerism of avobenzone (AVO) is pivotal to its photostability, influenced by microenvironmental factors, such as, the type of solvent and complexation with macrocyclic compounds. This study explores the effect of host–guest complexation on AVO photostabilization, employing cucurbit[7]uril (CB[7]) and β-cyclodextrin (β-CD) to form inclusion complexes. CB[7] exhibits a higher affinity to the keto form of AVO, a UVC radiation absorber. The complexed keto form facilitates the regeneration of the enol form, reducing skin permeation. Spectroscopic and thermal analyses confirm 1 : 1 AVO–CB[7] and AVO–β-CD complex formation. Computational and MD simulations show that host–guest complex is favored over isolated AVO and β-CD or CB[7] molecules by 95–125 kJ mol⁻¹, depending on the presence of implicit solvent. Both macrocycles enhance AVO photostabilization in aqueous environments, with CB[7] displaying greater selectivity for the keto form, while β-CD shows ethanol concentration-dependent binding.