Controlled assembly of OD supramolecular nanocages into 2D or 3D architectures has been demonstrated for the first time via a coordination-driven polymerization approach, and the conversion from a 2D to 3D supramolecular architecture has also been successfully achieved via a temperature-induced crystal transformation. The boost of dimensionality for the supramolecular architecture has led to steady yet remarkable enhancement of properties, as reflected from the gas adsorption studies.