The synthesis, spectroscopic characterization, and electrochemistry of 12 different neutral, singly and doubly oxidized heteroleptic double-decker complexes of the type [M^jPjjPc)]" where = 0, +1, or +2, M = Zr or Hf, P = the dianion of octaethylporphyrin (OEP) or tetraphenylporphyrin (TPP), and Pc = the dianion of phthalocyanine are reported. Each neutral compound was characterized by NMR, UV-visible, and IR spectroscopy while each oxidized or reduced compound was characterized by UV-visible and/or EPR spectroscopy. The neutral compounds all undergo two reversible ring-centered oxidations and two reversible ring-centered reductions.Comparison is made with data obtained for the corresponding actinide double-decker complexes containing Th(IV) or U(IV) central metal ions and correlations examined between £1/2 for all of the compounds and either the metal ionic radius or the absorbance band energy of the porphyrin Soret or phthalocyanine UV-band. The half-wave potentials depend upon the type of macrocycle. They also vary with the size of metal ion in the case of oxidation but not in reduction, where £1/2 values are relatively unaffected and shift by only 20-40 mV upon going from Hf(P)(Pc) to Th(P)(Pc) as compared to a much larger 220-280 mV shift between Em for the first oxidation of the same compounds.

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