title: Electronic Modulation of the SOMO-HOMO Energy Gap in Iron(III) Complexes towards Unimolecular Current Rectification.
abstract: Amphiphilic five-coordinate iron(III) complexes with {N2 O2 Cl} and {N2 O3 } coordination spheres are studied to elucidate the roles of electronic structure on the mechanisms for current rectification. The presence of an apical chlorido or phenolato ligand plays a crucial role, and the [Fe(III) {N2 O2 Cl}] species supports an asymmetric mechanism while its [Fe(III) {N2 O3 }] counterpart seems to allow for unimolecular mechanism. The effects of electron-donating and electron-withdrawing substituents in the ligand frameworks are also considered.
authors.affiliation: Department of Chemistry, Wayne State University, 5101 Cass Ave, Detroit, MI, 48202, USA.
authors.forename: Lanka D
authors.initials: LD
authors.lastname: Wickramasinghe
authors.affiliation: Department of Chemistry, Wayne State University, 5101 Cass Ave, Detroit, MI, 48202, USA.
authors.forename: Shivnath
authors.initials: S
authors.lastname: Mazumder
authors.affiliation: Department of Chemistry, Wayne State University, 5101 Cass Ave, Detroit, MI, 48202, USA.
authors.forename: Kenneth K
authors.initials: KK
authors.lastname: Kpogo
authors.affiliation: Department of Chemistry, Michigan State University, Lansing, MI, 48824, USA.
authors.forename: Richard J
authors.initials: RJ
authors.lastname: Staples
authors.affiliation: Department of Chemistry, Wayne State University, 5101 Cass Ave, Detroit, MI, 48202, USA.
authors.forename: H Bernhard
authors.initials: HB
authors.lastname: Schlegel
authors.affiliation: Department of Chemistry, Wayne State University, 5101 Cass Ave, Detroit, MI, 48202, USA. cnverani@chem.wayne.edu.
authors.forename: Cláudio N
authors.identifier: http://orcid.org/0000-0001-6482-1738
authors.initials: CN
authors.lastname: Verani
keywords: coordination complexes; current rectification mechanisms; electron transfer; iron; molecular rectification