Advancements in calixarene-protected titanium-oxo clusters: from structural assembly to catalytic functionality

Abstract

This review explores calixarenes, a prominent family of third-generation supramolecules celebrated for their distinct hollow, cavity-shaped structures. These macrocycles are intricately assembled by linking multiple phenolic units orthogonally through methylene (–CH₂–), sulfur (–S–), or sulfonyl (–SO₂–) bridges. This structural framework plays a pivotal role in the intricate assembly of nanoclusters, significantly advancing the field of cluster chemistry. A key focus of current research is the remarkable ability of calixarenes to stabilize titanium-oxo clusters. Our review details the application of calixarenes in constructing titanium-oxo cluster structures, emphasizing how these clusters, when encapsulated within calixarenes, exploit flexible coordination sites for structural modifications and serve as foundational units for more complex assemblies. Additionally, we investigate how these calixarene-stabilized metal-oxo clusters function as versatile scaffolds for catalytically active metal ions, facilitating the creation of bimetallic nanoclusters. These clusters not only exhibit unique structural diversity but also demonstrate exceptional catalytic efficiency. This review aims to inspire ongoing exploration and innovation in the use of calixarenes for the synthesis and application of advanced cluster materials.