Supramolecular assembly of metalloporphyrins in crystals by axial coordination through amine ligands

Axial coordination to metalloporphyrins is an important tool in the supramolecular chemistry of these entities. Metalated 5,10,15,20-tetraphenylporphyrins can be axially linked to each other with the aid of amine and diamine ligands. Seven new crystalline materials consisting of such heterogeneous coordination oligomers and polymers of Zn(II)- or Mn(III)-tetraphenylporphyrins have been prepared and characterized by X-ray crystallography. Ligands of varying length have been used as bridging auxiliaries between the metal centers of the porphyrin species, effecting heterogeneous porphyrin-ligand oligomeric as well as polymeric assemblies. These correspond, respectively, to "wheel-and-axle" and "shish-kebab" type shapes of the supramolecular scaffolds. In addition, a uniquely structured homogeneous coordination polymer of a Zn(II)-tetrapyridylporphyrin derivative, is also reported.