TY - JOUR
T1 - Thermally Induced Valence Tautomeric Transition in a Two-Dimensional Fe-Tetraoxolene Honeycomb Network
AU - Chen, Jian
AU - Sekine, Yoshihiro
AU - Komatsumaru, Yuki
AU - Hayami, Shinya
AU - Miyasaka, Hitoshi
N1 - Publisher Copyright:
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2018/9/10
Y1 - 2018/9/10
N2 - 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.
AB - 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.
KW - electron transfer
KW - layered compounds
KW - magnetic properties
KW - single-chain magnets
KW - valence tautomerism
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U2 - 10.1002/anie.201807556
DO - 10.1002/anie.201807556
M3 - Article
C2 - 30047197
AN - SCOPUS:85052753761
SN - 1433-7851
VL - 57
SP - 12043
EP - 12047
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 37
ER -