論文

査読有り
2019年9月

Paddlewheel-type diruthenium(III, III) tetrakis(2-aminopyridinate) complexes with NIR absorption features: combined experimental and theoretical study

DALTON TRANSACTIONS
  • Kataoka, Yusuke
  • ,
  • Imasaki, Nanako
  • ,
  • Arakawa, Kazuki
  • ,
  • Yano, Natsumi
  • ,
  • Sakiyama, Hiroshi
  • ,
  • Sugimori, Tamotsu
  • ,
  • Mitsumi, Minoru
  • ,
  • Handa, Makoto

48
33
開始ページ
12421
終了ページ
12429
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1039/c9dt02271f
出版者・発行元
ROYAL SOC CHEMISTRY

The reactions of [ Ru2(O2CCH3) 4Cl] with 2-aminopyridine (Hamp) and 2-amino-4-methylpyridine (Hammp) afforded two novel Ru2 complexes, [ Ru2(amp) 4Cl2] (1) and [ Ru2(ammp) 4Cl2] (2), respectively. Single crystal X-ray diffraction analyses revealed that 1 and 2 adopted typical paddlewheel-type structures, where the Ru2 units are coordinated with four aminopyridinate ligands with a cis-2: 2 arrangement at the equatorial positions and two chloride ligands at the axial positions. The stabilities of 1 and 2 were supported by unrestricted density functional theory (uDFT) calculations. The zero-point energies of the three structural isomers (trans-2: 2, 3: 1, and 4: 0 arrangements) of 1 and 2 were less stable than those of the respective cis-2: 2 arrangements. Temperature-dependences of the magnetic susceptibility measurements and uDFT calculations showed that the oxidation and spin states of the Ru2 units in 1 and 2 were commonly Ru2 6+ and triplet states, respectively. Cyclic voltammetry showed that 1 and 2 underwent oneelectron reduction processes, i. e., 1/1-and 2/2-, at redox potentials (E1/2) of -0.08 and -0.18 V vs. SCE, respectively. These results agreed well with the DFT-calculated E1/2 values of 1 (-0.08 V vs. SCE) and 2 (-0.18 V vs. SCE) and were theoretically attributed to Ru2-centred (d*(Ru2)) redoxes. Moreover, 1 and 2 showed unique near-infrared absorption bands at approximately 1200-1500 nm, which were theoretically attributed to the ligand-to-metal charge transfer (LMCT) with p(amp or ammp). d*(Ru2) transition characteristics.

リンク情報
DOI
https://doi.org/10.1039/c9dt02271f
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000481917100039&DestApp=WOS_CPL
ID情報
  • DOI : 10.1039/c9dt02271f
  • ISSN : 1477-9226
  • eISSN : 1477-9234
  • Web of Science ID : WOS:000481917100039

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