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 of 1H, 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.
Erickson, R., Holstrom, C., Rhoda, H., Rohde, G., Zatsikha, Y., Galloni, P., et al. (2017). 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. INORGANIC CHEMISTRY, 56, 4716-4727 [10.1021/acs.inorgchem.7b00397].
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
GALLONI, PIERLUCA;
2017-04-01
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 of 1H, 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.File | Dimensione | Formato | |
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