Crystal Engineering of “Porphyrin Sieves” Based on Coordination Polymers of Pd- and Pt-tetra(4-carboxyphenyl)porphyrin

Abstract

Targeted solid-state synthesis of supramolecular porphyrin networks with palladium- and platinum-tetra(4-carboxyphenyl)porphyrins as building blocks, in different reaction environments, afforded a series of new extended coordination polymers sustained by sodium, potassium, and copper metal ion cluster auxiliaries. Formulation of open channel-type architectures in these materials has been confirmed by X-ray crystallography at low temperature. Open, 0.50−0.65 nm wide, channels were found to propagate throughout the corresponding crystals. These channels are accessible to other guest/solvent molecules for inclusion in the crystalline lattice. The structural features of the analyzed materials resemble those of common molecular sieve solids, and represent a successful realization of the crystal engineering concepts of porphyrin-based supramolecular design evaluated in this laboratory.