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

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Abstract
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.

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