Synthesis and Characterization of a RuPt-Based Photo-Hydrogen-Evolving Molecular Device Tethered to a Single Viologen Acceptor

Masayuki Miyaji, Kyoji Kitamoto, Hironobu Ozawa, Ken Sakai

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Abstract

A dinuclear RuIIPtII complex tethered to a methyl viologen (MV2+) unit {RuPt-MV2+; [RuII(bpy)2{phen-bpy(MV2+)}PtIICl2]4+, bpy = 2,2′-bipyridine, phen = 5-amino-1,10-phenanthroline} has been synthesized to investigate the effect of tethering a single pendant MV2+ acceptor on its photo-hydrogen-evolving (PHE) activity. Upon photoirradiation of RuPt-MV2+ in the presence of EDTA as a sacrificial electron donor, the one-electron-reduced species of RuPt-MV2+ {i.e., [RuII(bpy)2{phen-bpy(MV)}PtIICl2]3+} is generated as a major photoproduct by intramolecular electron transfer (IET) from the 3MLCT excited state of the [RuII(bpy)2(phen)]2+ unit to the MV2+ unit, followed by subsequent reduction of the [RuIII(bpy)2(phen)]3+ unit by EDTA. Although RuPt-MV2+ shows PHE activity in the presence of EDTA, the estimated turnover number (0.4) is smaller than that for the parent RuIIPtII system, which has no MV2+ tether. The relatively small driving force (0.08 eV) for the IET from the 3MLCT excited state of the [RuII(bpy)2(phen)]2+ unit to the PtIICl2(bpy) unit, which leads to the H2 formation, has been judged to be the major cause of the exceptionally low PHE activity observed for the present system.

Original languageEnglish
Pages (from-to)1237-1244
Number of pages8
JournalEuropean Journal of Inorganic Chemistry
Volume2017
Issue number9
DOIs
Publication statusPublished - Mar 3 2017

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Viologens
Hydrogen
Edetic Acid
Electrons
Excited states
Paraquat

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

Synthesis and Characterization of a RuPt-Based Photo-Hydrogen-Evolving Molecular Device Tethered to a Single Viologen Acceptor. / Miyaji, Masayuki; Kitamoto, Kyoji; Ozawa, Hironobu; Sakai, Ken.

In: European Journal of Inorganic Chemistry, Vol. 2017, No. 9, 03.03.2017, p. 1237-1244.

Research output: Contribution to journalArticle

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