title: Self-assembly of heterobimetallic neutral macrocycles incorporating ferrocene spacer groups: spectroelectrochemical analysis of the double two-electron oxidation of a molecular rectangle.
abstract: Two Pt(4)-Fe(2) mixed-metal neutral assemblies, 4 and 5, 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 symmetrical heterobimetallic neutral species possessing a rhomboidal and rectangular shape, respectively. The rectangular molecules, 5, could be reversibly oxidized in two two-electron steps, separated by 0.21 V. Spectroelectrochemistry in the UV-vis-NIR region confirms the ferrocene groups as primary oxidation sites; however, the intermediate 5(2+) is EPR silent even at 4 K due to enhanced EPR relaxation involving the oxidizable 1,8-anthracenediyl linkers.
authors.affiliation: University of Utah, Department of Chemistry 315 South 1400 East, Salt Lake City, 84112, USA.
authors.forename: Neeladri
authors.initials: N
authors.lastname: Das
authors.forename: Atta M
authors.initials: AM
authors.lastname: Arif
authors.forename: Peter J
authors.initials: PJ
authors.lastname: Stang
authors.forename: Monika
authors.initials: M
authors.lastname: Sieger
authors.forename: Biprajit
authors.initials: B
authors.lastname: Sarkar
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Kaim
authors.forename: Jan
authors.initials: J
authors.lastname: Fiedler