Synthesis, Structure and Dye Adsorption Properties of Wine-Rack-Type Supramolecular Macrocycles Based on Polyoxovanadate

The precise construction and programmable assembly of structures with specific topologies remain persistent challenges in crystal engineering, primarily constrained by the limited availability of building blocks. Utilizing a synergistic approach that combines an in situ-formed concave polyoxovanadate (POV) cluster {VV₄} with specifically designed 120° ditopic carboxylic acid bridging ligands, we successfully synthesized a series of wine-rack-type supramolecular macrocycles characterized by the general formula [(V₅O₉Cl)₄(L)₈]^8-. The experimental results demonstrate that the introduction of sulfonic acid groups enables controlled structural extension into 1D chain and 2D layer architectures, manifesting the unique advantages of POV-based wine-rack units in constructing framework-based porous materials. This work significantly contributes to the structural diversity of wine-rack-type supramolecular architectures while simultaneously highlighting the great potential of polyoxometalate-driven supramolecular assemblies in materials science.