Heterometallic FeIII/K Coordination Polymer with a Wide Thermal Hysteretic Spin Transition at Room Temperature

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Abstract

The anionic FeIII complex exhibiting cooperative spin transition with a wide thermal hysteresis near room temperature, K[Fe(5-Brthsa)2] (5-Brthsa-H2=5-bromosalicylaldehyde thiosemicarbazone), is reported. The hysteresis (Δ=69 K in the first cycle) shows a one-step transition in heating mode and a two-step transition in cooling mode. X-ray structure analysis showed that the coexistence of hydrogen bond and cation-π interactions, as well as alkali metal coordination bonds, to give 2D coordination polymer structure. This result is contrary to previous reports of broad thermal hysteresis induced by coordination bonds of FeII spin crossover coordination polymers (with 1D/3D structures), and by strong intermolecular interactions in the molecular packing through π-π stacking or hydrogen-bond networks. As a consequence, the importance, or the very good suitability of alkali metal-based coordination bonds and cation-π interactions for communicating cooperative interactions in spin-crossover (SCO) compounds must be reconsidered.

Original languageEnglish
Pages (from-to)532-538
Number of pages7
JournalChemistry - A European Journal
Volume22
Issue number2
DOIs
Publication statusPublished - Jan 11 2016

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Alkali Metals
Hysteresis
Polymers
Alkali metals
Cations
Hydrogen bonds
Positive ions
Thiosemicarbazones
Temperature
Cooling
Heating
X rays
Hot Temperature
5-bromosalicylaldehyde

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

Cite this

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title = "Heterometallic FeIII/K Coordination Polymer with a Wide Thermal Hysteretic Spin Transition at Room Temperature",
abstract = "The anionic FeIII complex exhibiting cooperative spin transition with a wide thermal hysteresis near room temperature, K[Fe(5-Brthsa)2] (5-Brthsa-H2=5-bromosalicylaldehyde thiosemicarbazone), is reported. The hysteresis (Δ=69 K in the first cycle) shows a one-step transition in heating mode and a two-step transition in cooling mode. X-ray structure analysis showed that the coexistence of hydrogen bond and cation-π interactions, as well as alkali metal coordination bonds, to give 2D coordination polymer structure. This result is contrary to previous reports of broad thermal hysteresis induced by coordination bonds of FeII spin crossover coordination polymers (with 1D/3D structures), and by strong intermolecular interactions in the molecular packing through π-π stacking or hydrogen-bond networks. As a consequence, the importance, or the very good suitability of alkali metal-based coordination bonds and cation-π interactions for communicating cooperative interactions in spin-crossover (SCO) compounds must be reconsidered.",
author = "Soonchul Kang and Yoshihito Shiota and Akira Kariyazaki and Shinji Kanegawa and Kazunari Yoshizawa and Osamu Sato",
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TY - JOUR

T1 - Heterometallic FeIII/K Coordination Polymer with a Wide Thermal Hysteretic Spin Transition at Room Temperature

AU - Kang, Soonchul

AU - Shiota, Yoshihito

AU - Kariyazaki, Akira

AU - Kanegawa, Shinji

AU - Yoshizawa, Kazunari

AU - Sato, Osamu

PY - 2016/1/11

Y1 - 2016/1/11

N2 - The anionic FeIII complex exhibiting cooperative spin transition with a wide thermal hysteresis near room temperature, K[Fe(5-Brthsa)2] (5-Brthsa-H2=5-bromosalicylaldehyde thiosemicarbazone), is reported. The hysteresis (Δ=69 K in the first cycle) shows a one-step transition in heating mode and a two-step transition in cooling mode. X-ray structure analysis showed that the coexistence of hydrogen bond and cation-π interactions, as well as alkali metal coordination bonds, to give 2D coordination polymer structure. This result is contrary to previous reports of broad thermal hysteresis induced by coordination bonds of FeII spin crossover coordination polymers (with 1D/3D structures), and by strong intermolecular interactions in the molecular packing through π-π stacking or hydrogen-bond networks. As a consequence, the importance, or the very good suitability of alkali metal-based coordination bonds and cation-π interactions for communicating cooperative interactions in spin-crossover (SCO) compounds must be reconsidered.

AB - The anionic FeIII complex exhibiting cooperative spin transition with a wide thermal hysteresis near room temperature, K[Fe(5-Brthsa)2] (5-Brthsa-H2=5-bromosalicylaldehyde thiosemicarbazone), is reported. The hysteresis (Δ=69 K in the first cycle) shows a one-step transition in heating mode and a two-step transition in cooling mode. X-ray structure analysis showed that the coexistence of hydrogen bond and cation-π interactions, as well as alkali metal coordination bonds, to give 2D coordination polymer structure. This result is contrary to previous reports of broad thermal hysteresis induced by coordination bonds of FeII spin crossover coordination polymers (with 1D/3D structures), and by strong intermolecular interactions in the molecular packing through π-π stacking or hydrogen-bond networks. As a consequence, the importance, or the very good suitability of alkali metal-based coordination bonds and cation-π interactions for communicating cooperative interactions in spin-crossover (SCO) compounds must be reconsidered.

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U2 - 10.1002/chem.201503392

DO - 10.1002/chem.201503392

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JO - Chemistry - A European Journal

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SN - 0947-6539

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