Supramolecular Crystal Chemistry of Tetra(3-pyridyl)porphyrin. 2. Two- and Three-Dimensional Coordination Networks with Cobalt and Cadmium Ions

New hybrid coordination polymers have been self-assembled with the conformationally versatile tetra(3-pyridyl)-porphyrin ((TPyP)-Py-3) scaffold. Hydrothermal reactions with cobalt ions resulted in metalition of the porphyrin core and self-coordination of the (CoTPyP)-Py-3 units through their endocyclic metal centers into two-dimensional (2D) polymeric arrays. These crystallized into interdigitated, either solvent-free or N,N-dimethylformamide-solvated, structures. Interaction of the (TPyP)-Py-3 with cadmium ions yielded three-dimensional (3D) framework solids tessellated by exocyclic CdCl2 connectors to the peripheral pyridyl sites of neighboring units of either the freebase porphyrin or its (CdTPyP)-Py-3 analogue. The complementary tetradenate nature of the porphyrin linkers and CdCl2 nodes resulted in pseudodiamondoid polymerization schemes.