The synthesis of a novel family of heterobinuclear cofacial biphenylene (B), anthracene (A), 9,9-dimethylxanthene (X), or dibenzofuran (O) bridged porphyrin-corrole complexes, (PCY)MClCoCl, is reported, M being either an iron(Ill) or manganese(III) ion. Each complex was characterized by electrochemistry, mass spectrometry, UV-vis, IR, and electron spin resonance spectroscopy. Unlike previously examined biscobalt porphyrin-corrole dyads, the cobalt ion of the corrole moiety is present in a high-valence +4 oxidation state, as proven by electrochemistry, spectroelectrochemistry, and an X-ray diffraction study of (PCB)FeClCoCl, which shows the presence of a bound Cl- anion on the cobalt corrole. Structural data: (PCB)FeclCoCl(.)0.5(C7H16)(.)0.5(CH2Cl2)(.)2H(2)O, triclinic, space group P (1) over bar, a = 13.8463(3) angstrom, b = 16.8164(5) angstrom, c = 17.9072(6) angstrom, alpha = 93.780(1)degrees, beta = 111.143(1)degrees, gamma = 97,463(2)degrees, Z = 2.