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Modulation of Spin-Crossover Behavior in an Elongated and Flexible Hofmann-Type Porous Coordination Polymer

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Abstract

Three porous coordination polymers {Fe(dpa)[Pt(CN)4]·G·nH2O} (1-G; dpa = 1,2-di(4-pyridyl)ethane, G = dpa, bibenzyl (bbz) and stilbene (stb)) have been prepared by using a long and flexible ligand dpa. These compounds formed analogous 3-D elongated Hofmann-type frameworks based on 2-D planar layers extended by Pt–CN–Fe linkages with dpa as flexible pillar ligands. 1-dpa showed a characteristic three-step spin transition (ST) in the temperature range 180–240 K. The ST behavior was reversibly modulated by dehydration and hydration processes in keeping with the three steps. 1-bbz and 1-stb exhibited a gradual three-step ST over the range 80–200 K and an abrupt ST with T c = 163 K. The guest-dependent cooperativity of the ST behavior is discussed by considering the flexibility of the framework and guest molecules.

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Acknowledgments

This work was supported by a Grant-In-Aid for Science Research in a Priority Area “Coordination Programming (No. 22108512)” and a Grant-In-Aid for Scientific Research Program (No. 23245014) from the Ministry of Education, Culture, Sports, Science and Technology of Japan. R. O. is grateful to JSPS Research Fellowships for Young Scientists. The synchrotron radiation experiments were performed at BL44B2 in SPring-8 with the approval of RIKEN (Proposal No. 20110055).

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Authors and Affiliations

  1. Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto, 615-8510, Japan

    Ryo Ohtani, Masashi Arai & Susumu Kitagawa

  2. Quantum Order Research Group, RIKEN SPring-8 Center, Koto 1-1-1, Sayo-cho, Sayo, Hyogo, 679-5148, Japan

    Akihiro Hori, Masaki Takata, Susumu Kitagawa & Masaaki Ohba

  3. Research Reactor Institute, Kyoto University, 2, Asashiro-Nishi, Kumatori-cho, Sennan-gun, Osaka, 590-0494, Japan

    Shinji Kitao & Makoto Seto

  4. Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University, Yoshida, Sakyo-ku, Kyoto, 606-8501, Japan

    Susumu Kitagawa

  5. Department of Chemistry, Faculty of Science, Kyushu University, Hakozaki 6-10-1, Higashi-ku, Fukuoka, 812-8581, Japan

    Masaaki Ohba

Authors
  1. Ryo Ohtani
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Correspondence to Susumu Kitagawa or Masaaki Ohba.

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This paper is dedicated to Prof. Dr. Hiroshi Nishihara for his outstanding contribution to the field of metal-containing polymers.

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Ohtani, R., Arai, M., Hori, A. et al. Modulation of Spin-Crossover Behavior in an Elongated and Flexible Hofmann-Type Porous Coordination Polymer. J Inorg Organomet Polym 23, 104–110 (2013). https://doi.org/10.1007/s10904-012-9747-z

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