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Spin crossover behaviour in Hofmann-like coordination polymer Fe(py)2[Pd(CN)4] with 57Fe Mössbauer spectra

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Abstract

We have prepared the 2D spin crossover complexes Fe(L)2Pd(CN)4 (L = py : 1a; py-D5 : 1b and py-15N :1c). 1a has been characterised by 57Fe Mossbauer spectroscopic measurements, single crystal X-ray determination and SQUID measurements. The Mössbauer spectra for 1a indicate that the iron(II) spin states are in high spin states at 298 K and are in low spin states at 77 K. The crystal structures of 1a at 298 K and 90 K also show the high spin state and the low spin state respectively, associated with the Fe(II)-N distances. The spin transition temperature range of 1a is higher than that of Fe(py)2Ni(CN)4 since Pd(II) ions are larger and heavier than Ni(II) ions. SQUID data indicate isotope effects among 1a, 1b and 1c are observed in very small shifts of the transition temperatures probably due to larger and heavier Pd(II) ions. The delicate shifts would be associated with subtle balances between different vibrations around Fe(II) atoms and electronic factors.

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Acknowledgements

This work was supported by MEXT(Ministry of Education, Culture, Sports, Science and Technology, Japan)-Supported Program for the Strategic Research Foundation at Private Universities, 2012–2016. This work was also supported by JSPS KAKENHI Grant Number 15K05485.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, Toho University, 2-2-1 Miyama, Funabashi, Chiba, 274-8510, Japan

    Takafumi Kitazawa, Takanori Kishida, Takeshi Kawasaki & Masashi Takahashi

  2. Research Centre for Materials with Integrated Properties, Toho University, 2-2-1 Miyama, Funabashi, Chiba, 274-8510, Japan

    Takafumi Kitazawa & Masashi Takahashi

Authors
  1. Takafumi Kitazawa
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  2. Takanori Kishida
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  3. Takeshi Kawasaki
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  4. Masashi Takahashi
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Correspondence to Takafumi Kitazawa.

Additional information

This article is part of the Topical Collection on Proceedings of the 3rd Mediterranean Conference on the Applications of the Mössbauer Effect (MECAME 2017), Jerusalem, Israel, 5–7 June 2017

Edited by Mira Ristic, Stjepko Krehula, Israel Nowik and Israel Felner

This paper is dedicated to Prof. Rivka Bauminger and Prof. Rolfe Herber on the occasions of their 90 birthdays.

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Kitazawa, T., Kishida, T., Kawasaki, T. et al. Spin crossover behaviour in Hofmann-like coordination polymer Fe(py)2[Pd(CN)4] with 57Fe Mössbauer spectra. Hyperfine Interact 238, 65 (2017). https://doi.org/10.1007/s10751-017-1436-4

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