Host‐Guest Assemblies of Polyoxovanadate Clusters as Supramolecular Catalysts

Supramolecular functional materials can be used to overcome some of the most challenging tasks in materials science, where the dynamic nature of supramolecular interactions can be leveraged to fine‐tune the properties of the material. The Lindqvist hexavanadate family of polyoxometalates are interesting candidates for supramolecular materials due to their redox and Lewis acid properties that enable their application in energy conversion or catalysis. Despite their promising potential, hexavanadate clusters are underrepresented in supramolecular materials, mainly due to the synthetic challenges related to their inherent reactivity. In this work, pillar[5]arene was successfully grafted onto a Lindqvist hexavanadate and the resulting structure was confirmed by single crystal X‐ray diffraction, presenting the first example of a crystal structure of a polyoxometalate covalently functionalized with a pillar[5]arene. By introducing a ditopic guest molecule that could interlink pillar[5]arene moieties, host‐guest interactions were leveraged as the driving force for the formation of supramolecular assemblies incorporating hexavanadate clusters in a controlled manner. The enhanced catalytic performance of the resulting aggregates confirmed their potential application as functional catalytic materials. This novel approach for developing hexavanadate‐based catalysts reported here showcases the potential of using host‐guest interactions as a means to introduce catalytically active metal‐oxo clusters into supramolecular frameworks.