Characterization of redox states of Ru(OH 2)(Q)(tpy) 2+ (Q = 3,5-di-ferf-butyl-1,2-benzoquinone, tpy = 2,2′:6′, 2′′-terpyridine) and related species through experimental and theoretical studies

Ming-Kang Tsai, Jonathan Rochford, Dmitry E. Polyansky, Tohru Wada, Koji Tanaka, Etsuko Fujita, James T. Muckerman

Research output: Contribution to journalArticle

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Abstract

The redox states of Ru(OH 2)(Q)(tpy) 2+ (Q = 3,5-di-fert-butyl-l,2-benzoquinone, tpy = 2,2′:6′,2′′- terpyridine) are investigated through experimental and theoretical UV-vis spectra and Pourbalx diagrams. The electrochemical properties are reported for the species resulting from deprotonatlon and redox processes in aqueous solution. The formal oxidation states of the redox couples In the various Intermediate complexes are systematically assigned using electronic structure theory. The controversy over the electronic assignment of ferromagnetic vs. antiferromagnetic coupling Is investigated through comparison of ab Initio methods and the broken-symmetry density functional theory (DFT) approach. The various pK a values and reduction potentials, including the consideration of proton-coupled electron-transfer (PCET) processes, are calculated, and the theoretical version of the Pourbaix diagram is constructed In order to elucidate and assign several previously ambiguous regions In the experimental diagram.

Original languageEnglish
Pages (from-to)4372-4383
Number of pages12
JournalInorganic Chemistry
Volume48
Issue number10
DOIs
Publication statusPublished - 2009 May 18

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quinones
Oxidation-Reduction
Theoretical Models
diagrams
Electrochemical properties
Electronic structure
Density functional theory
Protons
Electrons
Oxidation
broken symmetry
electron transfer
density functional theory
electronic structure
aqueous solutions
oxidation
protons
2-benzoquinone
electronics

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Characterization of redox states of Ru(OH 2)(Q)(tpy) 2+ (Q = 3,5-di-ferf-butyl-1,2-benzoquinone, tpy = 2,2′:6′, 2′′-terpyridine) and related species through experimental and theoretical studies. / Tsai, Ming-Kang; Rochford, Jonathan; Polyansky, Dmitry E.; Wada, Tohru; Tanaka, Koji; Fujita, Etsuko; Muckerman, James T.

In: Inorganic Chemistry, Vol. 48, No. 10, 18.05.2009, p. 4372-4383.

Research output: Contribution to journalArticle

Tsai, Ming-Kang ; Rochford, Jonathan ; Polyansky, Dmitry E. ; Wada, Tohru ; Tanaka, Koji ; Fujita, Etsuko ; Muckerman, James T. / Characterization of redox states of Ru(OH 2)(Q)(tpy) 2+ (Q = 3,5-di-ferf-butyl-1,2-benzoquinone, tpy = 2,2′:6′, 2′′-terpyridine) and related species through experimental and theoretical studies. In: Inorganic Chemistry. 2009 ; Vol. 48, No. 10. pp. 4372-4383.
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abstract = "The redox states of Ru(OH 2)(Q)(tpy) 2+ (Q = 3,5-di-fert-butyl-l,2-benzoquinone, tpy = 2,2′:6′,2′′- terpyridine) are investigated through experimental and theoretical UV-vis spectra and Pourbalx diagrams. The electrochemical properties are reported for the species resulting from deprotonatlon and redox processes in aqueous solution. The formal oxidation states of the redox couples In the various Intermediate complexes are systematically assigned using electronic structure theory. The controversy over the electronic assignment of ferromagnetic vs. antiferromagnetic coupling Is investigated through comparison of ab Initio methods and the broken-symmetry density functional theory (DFT) approach. The various pK a values and reduction potentials, including the consideration of proton-coupled electron-transfer (PCET) processes, are calculated, and the theoretical version of the Pourbaix diagram is constructed In order to elucidate and assign several previously ambiguous regions In the experimental diagram.",
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