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Light-induced spin-crossover magnet

Nature Chemistry volume 3, pages 564–569 (2011)Cite this article

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Abstract

The light-induced phase transition between the low-spin (LS) and high-spin (HS) states of some transition-metal ions has been extensively studied in the fields of chemistry and materials science. In a crystalline extended system, magnetically ordering the HS sites of such transition-metal ions by irradiation should lead to spontaneous magnetization. Previous examples of light-induced ordering have typically occurred by means of an intermetallic charge transfer mechanism, inducing a change of valence of the metal centres. Here, we describe the long-range magnetic ordering of the extended FeII(HS) sites in a metal–organic framework caused instead by a light-induced excited spin-state trapping effect. The Fe–Nb-based material behaves as a spin-crossover magnet, in which a strong superexchange interaction (magnetic coupling through non-magnetic elements) between photo-produced FeII(HS) and neighbouring NbIV atoms operates through CN bridges. The magnetic phase transition is observed at 20 K with a coercive field of 240 Oe.

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Figure 1: Crystal structure of Fe2[Nb(CN)8]·(4-pyridinealdoxime)8·2H2O.
Figure 2: Spin-crossover transition phenomenon.
Figure 3: Photo-induced magnetization caused by light-induced spin-crossover.
Figure 4: Mechanism of light-induced spin-crossover ferromagnetism.

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Acknowledgements

The authors acknowledge support from the Core Research for Evolutional Science and Technology (CREST) project of JST, a Grant-in-Aid for Young Scientists (S) from JSPS, the Global COE Program, ‘Chemistry Innovation through Cooperation of Science and Engineering’ from MEXT Japan, the Photon Frontier Network Program from MEXT, the Izumi Science and Technology Foundation and the Asahi Glass Foundation. The authors are grateful to Kosuke Nakagawa, Koji Nakabayashi and Tomohiro Nuida for their assistance with measurements, and to Wataru Kosaka for help with the synthesis. Acknowledgements are also given to the Cryogenic Research Center, The University of Tokyo and the Center for Nano Lithography & Analysis, The University of Tokyo, supported by MEXT Japan.

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  1. Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan

    Shin-ichi Ohkoshi, Kenta Imoto, Yoshihide Tsunobuchi, Shinjiro Takano & Hiroko Tokoro

  2. CREST, JST, 5 Sanbancho, Chiyoda-ku, Tokyo, 102-0075, Japan

    Shin-ichi Ohkoshi

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Contributions

S.O. designed and coordinated this study, contributed to all measurements and calculations, and wrote the paper. K.I. carried out the synthesis, photo-irradiation measurements and Mössbauer spectroscopy. Y.T. conducted Rietveld analysis. S.T. performed the synthesis and elemental analysis. H.T. carried out photo-irradiation measurements and molecular-field calculations. All authors commented on the manuscript.

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Correspondence to Shin-ichi Ohkoshi.

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Crystallographic data for the Mn-Nb-based metal-organic framework (CIF 24 kb)

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Crystallographic data for the Fe-Nb-based metal-organic framework (CIF 13 kb)

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Ohkoshi, Si., Imoto, K., Tsunobuchi, Y. et al. Light-induced spin-crossover magnet. Nature Chem 3, 564–569 (2011). https://doi.org/10.1038/nchem.1067

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