The 5,10,15,20-tetraphenyl-21-oxaporphyrin complexes of Mn(II), Co(II), and Zn(II) have been crystallized and studied by X-ray diffraction, NMR and UV/vis spectroscopy, and mass spectrometry as well as cyclic voltammetry. The X-ray structure of the earlier described Cu(II) complex is also reported. All complex structures possess a five-coordinate, approximately square-pyramidal geometry with a slight deviation of the heteroaromatic moieties from planarity. The packing structures are characterized by parallel strands of complex molecules interacting by weak hydrogen bonds. In the case of Zn(II) an octahedral complex has also been isolated using a side-chain hydroxy functionalized oxaporphyrin ligand; the structure was verified by NMR and EXAFS spectroscopy. Cyclic voltammetry studies reveal that the reduction of the complex bound Mn(II), Co(II), and Zn(II) ions is a ligand-centered process whereas the first oxidation step depends on the metal ion present.

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