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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)MCICoCl, is reported, M being either an iron(III) or manganese(III) ion. Each complex is characterized by electrochemistry, mass spectrometry, UV-vis, IR, and electron spin resonance spectroscopy.

Research has been conducted on the cofacial biscorroles and linked Co(II) porphyrins and Co(III) corroles. The synthesis and characterization of these compounds with the same face to face orientation are discussed.

The first reproducible synthetic route to a UO(sub 2)(super +) coordination complex via a two-electron oxidation of U(III) and the first structurally characterized dioxouranium(V) halide that is found to form a one-dimensional (1D) coordination polymer in the presence of potassium iodide is described. The characteristic visible-NIR bands and the infrared UO(sub 2) asymmetric stretching frequency of the resultant green pyridine solution of the salophen complex have agreed with the presence of a pentavalent uranyl species confirming the versatility of the compound as a reagent for the preparation of new uranyl(V) complexes.

Three face-to-face linked porphyrin-corrole dyads are investigated as to their electrochemistry, spectroelectrochemistry, and chloride-binding properties in dichloromethane or benzonitrile. An axial binding of one or two Cl(super -) ligands to the cobalt center of the corrole is observed for singly and doubly oxidized (PCY)H2Co, with the exact stoichiometry of the reaction depending upon the spacer size and the concentration of Cl(super -) added to solution.

Three series of cobalt(III) corroles were tested as catalysts for the electroreduction of dioxygen to water. Cyclic voltammetry and rotating ring-disk electrode voltammetry were both used to examine the catalytic activity of the cobalt complexes in acid media.

The reaction of {[U[O.sub.2][Py.sub.5][[K].sub.2-][Py.suib.2]}.sub.n] polymer is investigated. The findings expand the scope for the preparation of polymetallic assemblies involving f-elements and a rich chemistry can be anticipated from the reaction of pentavalent uranyl with different metal cations.