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Electron-transfer processes in metal-free tetraferrocenylporphyrin. Understanding internal interactions to access mixed-valence States potentially useful for quantum cellular automata

Nemykin, Victor N. and Rohde, Gregory T. and Barrett, Christopher D. and Hadt, Ryan G. and Bizzarri, Claudia and Galloni, Pierluca and Floris, Barbara and Nowik, Israel and Herber, Rolfe H. and Marrani, Andrea G. and Zanoni, Robertino and Loim, Nikolay M. (2009) Electron-transfer processes in metal-free tetraferrocenylporphyrin. Understanding internal interactions to access mixed-valence States potentially useful for quantum cellular automata. Journal of the American Chemical Society, 131 (41). pp. 14969-14978. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20180612-155637465

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Abstract

Redox properties of H_2TFcP [TFcP^(2-) = 5,10,15,20-tetraferrocenylporphyrin^(2-)] were investigated using cyclic voltammetry, differential pulse voltammetry, and square-wave voltammetry methods in a large variety of solvents and electrolytes. When DMF, THF, and MeCN were used with TBAP as the supporting electrolyte, the first oxidation wave was assigned to a single four-electron oxidation process reflecting simultaneous oxidation of all iron(II) centers into iron(III) centers in H_2TFcP. When an o-DCB (1,2-dichlorobenzene)/TBAP combination was used in electrochemical experiments, four ferrocene substituents underwent two very diffuse, "two-electron" stepwise oxidations. The use of a weakly coordinating TFAB ([NBu_4][B(C_6F_5)_4]) electrolyte in o-DCB or DCM results in four single-electron oxidation processes for ferrocene substituents in which the first and second single-electron waves have a relatively large separation, while the second, third, and fourth oxidation processes are more closely spaced; similar results were observed when a DCM/TBAP system and an imidazolium cation-based ionic liquid ((bmim)Tf_2N = N-butyl-N'-methylimidazolium bis(trifluoromethanesulfonyl)imide) were used. Spectroelectrochemical oxidation of H_2TFcP in o-DCB or DCM with TFAB as the supporting electrolyte allowed for characterization of the mixed-valence [H_2TFcP]^+, [H_2TFcP]^(2+), and [H_2TFcP]^(3+) compounds by UV-vis spectroscopy in addition to the "all-Fe(III)" [H_2TFcP]^(4+). The chemical oxidation of H_2TFcP was tested using a variety of oxidants which resulted in formation of mixed-valence [H_2TFcP]^+ and [H_2TFcP]^(2+) as well as [H_2TFcP]^(4+), which were characterized by UV-vis-NIR, MCD, IR, Mossbauer, and XPS spectroscopy. The intervalence-charge-transfer bands observed in the near-IR region in [H_2TFcP]^+ and [H_2TFcP]^(2+) complexes were analyzed using Hush formalism and found to be of class II (in Robin-Day classification) character with localized ferrous and ferric centers. Class II behavior of [H_2TFcP]^+ and [H_2TFcP]^(2+) complexes was further confirmed by Mossbauer, IR, and XPS data.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/ja905310hDOIArticle
https://pubs.acs.org/doi/suppl/10.1021/ja905310hPublisherSupporting Information
ORCID:
AuthorORCID
Hadt, Ryan G.0000-0001-6026-1358
Additional Information:© 2009 American Chemical Society. Received July 1, 2009. Generous support from the NSF (Grant CHE-0809203) and Minnesota Supercomputing Institute to V.N.N. as well as University of Minnesota—Duluth Undergraduate Research Opportunity Grants to R.G.H. and C.B. is greatly appreciated. We also thank Dr. N. Kobayashi for the possibility to collect preliminary MCD data on H_2TFcP and Dr. R. Belosludov for help with the DFT calculations.
Funders:
Funding AgencyGrant Number
NSFCHE-0809203
Minnesota Supercomputing InstituteUNSPECIFIED
University of Minnesota DuluthUNSPECIFIED
Issue or Number:41
Record Number:CaltechAUTHORS:20180612-155637465
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180612-155637465
Official Citation:Electron-Transfer Processes in Metal-Free Tetraferrocenylporphyrin. Understanding Internal Interactions To Access Mixed-Valence States Potentially Useful for Quantum Cellular Automata Victor N. Nemykin, Gregory T. Rohde, Christopher D. Barrett, Ryan G. Hadt, Claudia Bizzarri, Pierluca Galloni, Barbara Floris, Israel Nowik, Rolfe H. Herber, Andrea G. Marrani, Robertino Zanoni, and Nikolay M. Loim Journal of the American Chemical Society 2009 131 (41), 14969-14978 DOI: 10.1021/ja905310h
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:87037
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:12 Jun 2018 23:11
Last Modified:03 Oct 2019 19:51

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