Abstract
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 {VV(4)} 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 [(V(5)O(9)Cl)(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.