Comparative study of metal-porphyrins, -porphyrazines, and -phthalocyanines.

A theoretical comparative study of complexes of porphyrin (P), porphyrazine (Pz), and phthalocyanine (Pc) with metal (M) = Fe, Co, Ni, Cu, and Zn has been carried out using a DFT method. The calculations provide a clear elucidation of the ground states for the MP/Pz/Pc molecules and for a series of [MP/Pz/Pc](x-) and [MP/Pz/Pc](y+) ions (x = 1, 2, 3, 4; y = 1, 2). There are significant differences among MP, MPz, and MPc in the electronic structure and other calculated properties. For FeP/Pz and CoP/Pz, the first oxidation occurs at the central metal, while it is the macroring of FePc and CoPc that is the site of oxidation. The smaller coordination cavity results in a stronger ligand field in Pz than in P. However, the benzo annulation produces a surprisingly strong destabilizing effect on the metal-macrocycle bonding. The effects of Cl axial bonding upon the electronic structures of the iron(III) complexes of P, Pz, and Pc were examined, as was the bonding of pyridine (py) to NiP, NiPz, and NiPc. The porphinato core size plays a crucial role in controlling the spin state of Fe(III) in these complexes. FePc(Cl) is predicted to be a pure intermediate-spin system, whereas NiPz(py)(2) and NiPc(py)(2) are metastable in high-spin (S = 1) states. The NiPz/Pc-(py)(2) binding energy curve has only a shallow well that facilitates decomposition of the complex. The NiP-(py)(2) bond energy is small, but the relatively deep well in the binding energy curve ought to make this system stable to decomposition. Copyright 2002 Wiley Periodicals, Inc. J Comput Chem 23: 1391-1403, 2002