Synthesis, crystal structure, spectroscopic and electrochemical properties, and H 2 -evolving activity of a new [PtCl(terpyridine)] + derivative with viologen-like redox properties

Masayuki Kobayashi, Shigeyuki Masaoka, Ken Sakai

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

A new Pt(ii)-based metalloviologen analog, [PtCl(Mepytpy)] 2+ (abbreviated as PV 2+ ; Mepytpy + = 4′-(4-methyl- pyridinio)-2,2′:6′,2′′-terpyridine), was synthesized and its spectroscopic and electrochemical properties were investigated. The structures of Mepytpy + and PV 2+ were solved by single-crystal X-ray diffraction analysis. Electrochemical studies in DMF (N,N-dimethylformamide) revealed that both the first and second reduction potentials of PV 2+ (E11/2 = -0.87 V vs. Fc/Fc + for PV 2+ /PV + ; E21/2 = -1.31 V vs. Fc/Fc + for PV + /PV 0 ) are nearly consistent with those of methylviologen (N,N′-dimetyl-4,4′-bipyridinium, MV 2+ ) (E11/2 = -0.90 V vs. Fc/Fc + for MV 2+ /MV + ; E21/2 = -1.28 V vs. Fc/Fc + for MV + /MV 0 ), where the first reduction of PV 2+ is assigned as the reduction at the Mepytpy + ligand bound to the Pt(ii) ion. Upon the addition of a reducing agent Na 2 S 2 O 4 into an aqueous acetate buffer solution (pH = 5.0) of PV 2+ , the generation of one-electron-reduced radical species (PV + ) was spectrophotometrically observed and was assigned based on the time-dependent density functional theory (TD-DFT) calculations. The H 2 -evolving activity of PV 2+ was evaluated in the presence of a sacrificial electron donor (EDTA) in an aqueous acetate buffer solution (pH = 5.0). It was found that the stability of the metalloviologen PV 2+ during the photolysis is much higher than that of the parent compound [PtCl(tpy)] + .

Original languageEnglish
Pages (from-to)4903-4911
Number of pages9
JournalDalton Transactions
Volume41
Issue number16
DOIs
Publication statusPublished - Apr 28 2012

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Viologens
Electrochemical properties
Crystal structure
Derivatives
Buffers
Acetates
Dimethylformamide
Electrons
Reducing Agents
Photolysis
Edetic Acid
X ray diffraction analysis
Density functional theory
Single crystals
Ions
Ligands
Oxidation-Reduction

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

Synthesis, crystal structure, spectroscopic and electrochemical properties, and H 2 -evolving activity of a new [PtCl(terpyridine)] + derivative with viologen-like redox properties . / Kobayashi, Masayuki; Masaoka, Shigeyuki; Sakai, Ken.

In: Dalton Transactions, Vol. 41, No. 16, 28.04.2012, p. 4903-4911.

Research output: Contribution to journalArticle

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abstract = "A new Pt(ii)-based metalloviologen analog, [PtCl(Mepytpy)] 2+ (abbreviated as PV 2+ ; Mepytpy + = 4′-(4-methyl- pyridinio)-2,2′:6′,2′′-terpyridine), was synthesized and its spectroscopic and electrochemical properties were investigated. The structures of Mepytpy + and PV 2+ were solved by single-crystal X-ray diffraction analysis. Electrochemical studies in DMF (N,N-dimethylformamide) revealed that both the first and second reduction potentials of PV 2+ (E11/2 = -0.87 V vs. Fc/Fc + for PV 2+ /PV + ; E21/2 = -1.31 V vs. Fc/Fc + for PV + /PV 0 ) are nearly consistent with those of methylviologen (N,N′-dimetyl-4,4′-bipyridinium, MV 2+ ) (E11/2 = -0.90 V vs. Fc/Fc + for MV 2+ /MV + ; E21/2 = -1.28 V vs. Fc/Fc + for MV + /MV 0 ), where the first reduction of PV 2+ is assigned as the reduction at the Mepytpy + ligand bound to the Pt(ii) ion. Upon the addition of a reducing agent Na 2 S 2 O 4 into an aqueous acetate buffer solution (pH = 5.0) of PV 2+ , the generation of one-electron-reduced radical species (PV + ) was spectrophotometrically observed and was assigned based on the time-dependent density functional theory (TD-DFT) calculations. The H 2 -evolving activity of PV 2+ was evaluated in the presence of a sacrificial electron donor (EDTA) in an aqueous acetate buffer solution (pH = 5.0). It was found that the stability of the metalloviologen PV 2+ during the photolysis is much higher than that of the parent compound [PtCl(tpy)] + .",
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