A functional zeolite analogue assembled from metalloporphyrins

The assembly of molecular building blocks with metal ions generating microporous network solids has been the focus of intense activity. Because of their potential applications associated with channels and cavities, such materials have been examined for size- and shape-selective catalysis, separations, sensors, molecular recognition and nanoscale reactors. Within this context, assemblies of robust and chemically versatile porphyrin and metalloporphyrin building blocks remain rare. Supramolecular architectures of porphyrin solids based on weak van der Waals interactions, hydrogen bonding and metal-ligand coordination networks have been reported. Although there are frequent allusions to zeolite-like microporosity from crystallography and loss of initial guest solvent molecules, evidence of functional microporous behaviour is scarce. We have demonstrated repeatable sorption-desorption with high selectivity on the basis of size, shape and functional group of the sorbate by a microporous metalloporphyrin solid in analogy to zeolites.