TY - JOUR
T1 - Three Distinct Redox States of an Oxo-Bridged Dinuclear Ruthenium Complex
AU - Yoshida, Masaki
AU - Kondo, Mio
AU - Nakamura, Toshikazu
AU - Sakai, Ken
AU - Masaoka, Shigeyuki
N1 - Funding Information:
This work was supported by a Grant-in-Aid for Young Scientists (A) (No. 25708011; to S.M.), a Grant-in-Aid for Challenging Exploratory Research (No. 26620160; to S.M.), a Grant-in-Aid for Young Scientists (B) (No. 24750140; to M.K.), and a Grant-in-Aid for Young Scientists (Start-up) (No. 25888023; to M.Y.) from the Japan Society for the Promotion of Science. This work was also supported by a Grant-in-Aid for Scientific Research on Innovative Areas "AnApple" (No. 25107526). M.Y. is grateful to the Research Fellowships of the Japan Society for the Promotion of Science for Young Scientists (No. 223656). The computations were performed using the Research Center for Computational Science, Okazaki (Japan). The authors thank Prof. Hidehiro Sakurai and Mr. Yuki Okabe [Institute for Molecular Science (Japan)] for the measurement of UV-visible-NIR absorption spectra.
Publisher Copyright:
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2014/10/1
Y1 - 2014/10/1
N2 - A series of [{(terpy)(bpy)Ru}(μ-O){Ru(bpy)(terpy)}]n+ ([RuORu]n+, terpy=2,2′;6′,2′′-terpyridine, bpy=2,2′-bipyridine) was systematically synthesized and characterized in three distinct redox states (n=3, 4, and 5 for RuII,III2, RuIII,III2, and RuIII,IV2, respectively). The crystal structures of [RuORu]n+ (n=3, 4, 5) in all three redox states were successfully determined. X-ray crystallography showed that the Ru O distances and the Ru-O-Ru angles are mainly regulated by the oxidation states of the ruthenium centers. X-ray crystallography and ESR spectra clearly revealed the detailed electronic structures of two mixed-valence complexes, [RuIIIORuIV]5+ and [RuIIORuIII]3+, in which each unpaired electron is completely delocalized across the oxo-bridged dinuclear core. These findings allow us to understand the systematic changes in structure and electronic state that accompany the changes in the redox state.
AB - A series of [{(terpy)(bpy)Ru}(μ-O){Ru(bpy)(terpy)}]n+ ([RuORu]n+, terpy=2,2′;6′,2′′-terpyridine, bpy=2,2′-bipyridine) was systematically synthesized and characterized in three distinct redox states (n=3, 4, and 5 for RuII,III2, RuIII,III2, and RuIII,IV2, respectively). The crystal structures of [RuORu]n+ (n=3, 4, 5) in all three redox states were successfully determined. X-ray crystallography showed that the Ru O distances and the Ru-O-Ru angles are mainly regulated by the oxidation states of the ruthenium centers. X-ray crystallography and ESR spectra clearly revealed the detailed electronic structures of two mixed-valence complexes, [RuIIIORuIV]5+ and [RuIIORuIII]3+, in which each unpaired electron is completely delocalized across the oxo-bridged dinuclear core. These findings allow us to understand the systematic changes in structure and electronic state that accompany the changes in the redox state.
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U2 - 10.1002/anie.201406443
DO - 10.1002/anie.201406443
M3 - Article
C2 - 25196840
AN - SCOPUS:84908071526
SN - 1433-7851
VL - 53
SP - 11519
EP - 11523
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 43
ER -