Solid-state supramolecular chemistry of porphyrins. Hydrogen-bonded networks and porous crystals ofmeso-tetra[4-(3,5-diaminotriazino)phenyl]porphyrin

Tesselation of new porphyrin-based network motifs was demonstrated in crystals by incorporation of the diaminotriazine functions in the molecular building blocks. The title compound was synthesized and successfully applied in the construction of a uniquely structured solid which consists of flat multiporphyrin networks with very large voids, 2.2 × 2.2 nm2. These assemblies mutually interpenetrate each other, yielding a spectacular concatenated arrangement sustained in three dimensions by cooperative hydrogen bonding. The resulting multiporphyrin architecture resembles a molecular-sieve material, having 0.6 nm wide channels which propagate through the crystal and are accessible to other molecules.