title: Tuning Electron-Transfer Properties in 5,10,15,20-Tetra(1'-hexanoylferrocenyl)porphyrins as Prospective Systems for Quantum Cellular Automata and Platforms for Four-Bit Information Storage.
abstract: Metal-free (1) and zinc (2) 5,10,15,20-tetra(1'-hexanoylferrocenyl)porphyrins were prepared using an acid-catalyzed tetramerization reaction between pyrrole and 1'-(1-hexanoyl)ferrocencarboxaldehyde. New organometallic compounds were characterized by combination of1H,13C, and variable-temperature NMR, UV-vis, magnetic circular dichroism, and high-resolution electrospray ionization mass spectrometry methods. The redox properties of 1 and 2 were probed by electrochemical (cyclic voltammetry and differential pulse voltammetry), spectroelectrochemical, and chemical oxidation approaches coupled with UV-vis-near-IR and Mössbauer spectroscopy. Electrochemical data recorded in the dichloromethane/TBA[B(C6F5)4] system (TBA[B(C6F5)4] is a weakly coordinating tetrabutylammonium tetrakis(pentafluorophenyl)borate electrolyte) are suggestive of "1e-+ 1e-+ 2e-" oxidation sequence for four ferrocene groups in 1 and 2, which followed by oxidation process centered at the porphyrin core. The separation between all ferrocene-centered oxidation electrochemical waves is very large (510-660 mV). The nature of mixed-valence [1]n+and [2]n+(n = 1 or 2) complexes was probed by the spectroelectrochemical and chemical oxidation methods. Analysis of the intervalence charge-transfer band in [1]+and [2]+is suggestive of the Class II (in Robin-Day classification) behavior of all mixed-valence species, which correlate well with Mössbauer data. Density functional theory-polarized continuum model (DFT-PCM) and time-dependent (TD) DFT-PCM methods were applied to correlate redox and optical properties of organometallic complexes 1 and 2 with their electronic structures.
authors.affiliation: Department of Chemistry & Biochemistry, University of Minnesota Duluth , Duluth, Minnesota 55812, United States.
authors.forename: Nathan R
authors.initials: NR
authors.lastname: Erickson
authors.affiliation: Department of Chemistry & Biochemistry, University of Minnesota Duluth , Duluth, Minnesota 55812, United States.
authors.forename: Cole D
authors.initials: CD
authors.lastname: Holstrom
authors.affiliation: Department of Chemistry & Biochemistry, University of Minnesota Duluth , Duluth, Minnesota 55812, United States.
authors.forename: Hannah M
authors.initials: HM
authors.lastname: Rhoda
authors.affiliation: Department of Chemistry & Biochemistry, University of Minnesota Duluth , Duluth, Minnesota 55812, United States.
authors.forename: Gregory T
authors.initials: GT
authors.lastname: Rohde
authors.affiliation: Department of Chemistry & Biochemistry, University of Minnesota Duluth , Duluth, Minnesota 55812, United States.|Department of Chemistry, University of Manitoba , Winnipeg, MB R3T 2N2, Canada.
authors.forename: Yuriy V
authors.initials: YV
authors.lastname: Zatsikha
authors.affiliation: Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma "Tor Vergata" , via Della Ricerca Scientifica, 00133 Rome, Italy.
authors.forename: Pierluca
authors.identifier: http://orcid.org/0000-0002-0941-1354
authors.initials: P
authors.lastname: Galloni
authors.affiliation: Department of Chemistry & Biochemistry, University of Minnesota Duluth , Duluth, Minnesota 55812, United States.|Department of Chemistry, University of Manitoba , Winnipeg, MB R3T 2N2, Canada.
authors.forename: Victor N
authors.identifier: http://orcid.org/0000-0003-4345-0848
authors.initials: VN
authors.lastname: Nemykin