Self-Assembly of Heterobimetallic Neutral Macrocycles Incorporating Ferrocene Spacer Groups: Spectroelectrochemical Analysis of the Double Two-Electron Oxidation of a Molecular Rectangle

, , , , , , and . Inorganic Chemistry 44 (16): 5798--5804 (2005)


Two Pt4-Fe2 mixed-metal neutral assemblies, incorporating four bis(triethylphosphine)platinum(II) centers, two flexible bridging 1,1'-ferrocenedicarboxylates, and two rigid 2,9-phenanthrenediyl (4) or 1,8-anthracenediyl (5) bridges, have been synthesized. X-ray characterization of 4 and 5 reveals the formation of discrete and highly sym. heterobimetallic neutral species possessing a rhomboidal and rectangular shape, resp. The rectangular mols., 5, could be reversibly oxidized in two two-electron steps, sepd. by 0.21 V. Spectroelectrochem. in the UV-vis-NIR region confirms the ferrocene groups as primary oxidn. sites; however, the intermediate 52+ is EPR silent even at 4 K due to enhanced EPR relaxation involving the oxidizable 1,8-anthracenediyl linkers. on SciFinder(R)

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