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 (T3PyP) scaffold. Hydrothermal reactions with cobalt ions resulted in metalation of the porphyrin core and self-coordination of the CoT3PyP 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 T3PyP 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 CdT3PyP analogue. The complementary tetradenate nature of the porphyrin linkers and CdCl2 nodes resulted in pseudodiamondoid polymerization schemes.