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On/off spin-crossover phenomenon and control of the transition temperature in assembled Iron(II) complexes

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Abstract

The present study reveals the on/off of spin-crossover (SCO) phenomenon in assembled Fe(II) complexes bridged by bis(pyridyl) type ligand. Whether SCO phenomenon occurs or not in assembled Fe(II) complexes bridged by bis(pyridyl) type ligand is determined by local structure around iron atom. SCO phenomenon occurs when the coordinating pyridines facing to each other across the iron atom are propeller type, while the phenomenon does not occur when they are parallel type or distorted propeller type. DFT calculation explained that, in the shortening of Fe-pyridine bonds when changing from high-spin state to low-spin state, the pyridines of propeller type can approach the iron atom with smaller steric hindrance than those of parallel and distorted propeller type complexes. The local structure is controlled by introducing methyl substituent and introducing π-system, changing SCO phenomenon. And the transition temperature of SCO is also controlled in assembled complexes bridged by 1,2-bis(4-pyridyl)ethane by mixing anionic ligand.

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Authors and Affiliations

  1. Natural Science Center for Basic Research and Development, Hiroshima University, 1-4-2, Kagamiyama, Higashi-Hiroshima, 739-8526, Japan

    Satoru Nakashima

  2. Graduate School of Science, Hiroshima University, 1-3-1, Kagamiyama, Higashi-Hiroshima, 739-8526, Japan

    Satoru Nakashima, Keisuke Yoshinami & Saki Iwai

  3. Nuclear Science and Engineering Center, Japan Atomic Energy Agency, 2-4, Shirakata, Tokaimura, 319-1195, Japan

    Masashi Kaneko

  4. Graduate School of Engineering, Hiroshima University, 1-4-1, Kagamiyama, Higashi-Hiroshima, 739-8526, Japan

    Haruka Dote

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  1. Satoru Nakashima
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  2. Masashi Kaneko
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Correspondence to Satoru Nakashima.

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This article is part of the Topical Collection on Proceedings of the 4th Mediterranean Conference on the Applications of the Mössbauer Effect (MECAME 2018), Zadar, Croatia, 27-31 May 2018

Edited by Mira Ristic and Stjepko Krehula

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Nakashima, S., Kaneko, M., Yoshinami, K. et al. On/off spin-crossover phenomenon and control of the transition temperature in assembled Iron(II) complexes. Hyperfine Interact 239, 39 (2018). https://doi.org/10.1007/s10751-018-1512-4

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