Thermally Induced Valence Tautomeric Transition in a Two-Dimensional Fe-Tetraoxolene Honeycomb Network

Jian Chen, Yoshihiro Sekine, Yuki Komatsumaru, Shinya Hayami, Hitoshi Miyasaka

Research output: Contribution to journalArticlepeer-review

38 Citations (Scopus)


A novel tetraoxolene-bridged Fe two-dimensional honeycomb layered compound, (NPr4)2[Fe2(Cl2An)3] ⋅2 (acetone)⋅H2O (1), where Cl2Ann−=2,5-dichloro-3,6-dihydroxy-1,4-benzoquinonate and NPr4 +=tetrapropylammonium cation, has been synthesized. 1 revealed a thermally induced valence tautomeric transition at T1/2=236 K (cooling)/237 K (heating) between Fem+ (m=2 or 3) and Cl2Ann− (n=2 or 3) that induced valence modulations between [FeII HSFeIII HS(Cl2An2−)2(Cl2An.3−)]2− at T>T1/2 and [FeIII HSFeIII HS(Cl2An2−)(Cl2An.3−)2]2− at T<T1/2. Even in a two-dimensional network structure, the low-temperature phase [FeIII HSFeIII HS(Cl2An2−)(Cl2An.3−)2]2− valence set can be regarded as a magnetic chain-knit network, where ferrimagnetic Δ and Λ chains of [FeIII HS(Cl2An.3−)] are alternately linked by the diamagnetic Cl2An2−. This results in a slow magnetization behavior attributed to the structure acting as a single-chain magnet at lower temperatures.

Original languageEnglish
Pages (from-to)12043-12047
Number of pages5
JournalAngewandte Chemie - International Edition
Issue number37
Publication statusPublished - 2018 Sep 10


  • electron transfer
  • layered compounds
  • magnetic properties
  • single-chain magnets
  • valence tautomerism

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)


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