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Three-way switching in a cyanide-bridged [CoFe] chain

Nature Chemistry volume 4, pages 921–926 (2012)Cite this article

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Abstract

Bistable compounds that exist in two interchangeable phases under identical conditions can act as switches under external stimuli. Among such switchable materials, coordination complexes have energy levels (or phases) that are determined by the electronic states of their constituent metal ions and ligands. They can exhibit multiple bistabilities and hold promise in the search for multifaceted materials that display different properties in different phases, accessible through the application of contrasting external stimuli. Molecular systems that exhibit both thermo- and photoinduced magnetic bistabilities are excellent candidates for such systems. Here we describe a cyanide-bridged [CoFe] one-dimensional chiral coordination polymer that displays both magnetic and electric bistabilities in the same temperature range. Both the electric and magnetic switching probably arise from the same electron-transfer coupled spin-transition phenomenon, which enables the reversible conversion between an insulating diamagnetic phase and either a semiconducting paramagnetic (thermoinduced) or a type of ferromagnetic single-chain magnet (photoinduced) state.

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Figure 1: The heterometallic cyanide-bridged [CoFe] complex 1 with a square-wave type of structure.
Figure 2: Magnetic susceptibility data collected for 1·3H2O (red) and 1·H2O (blue) above 240 K.
Figure 3: Mössbauer spectra of 1·H2O at 293 K (top) and 265 K (middle), and of 1·3H2O at 20 K (bottom).
Figure 4: Light-induced magnetic susceptibility data of 1·H2O.
Figure 5: Temperature dependences of the d.c. conductivity (red) and magnetic susceptibility (blue) of 1·H2O in the thermal ETCST region.
Figure 6: Dielectric constant (ɛ′) and dielectric loss (ɛ′′) versus frequency plots (f = 500 Hz to 1 MHz) of 1·H2O measured between 310 and 255 K.

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Acknowledgements

This work was supported by a Grant-in-Aid for Scientific Research on Innovative Areas (‘Coordination Programming’ Area 2107, No. 21108006) from the Ministry of Education, Culture, Sports, Science and Technology, Japan, and by a research grant (No. 10K0028) from KEK.

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Authors and Affiliations

  1. Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tennodai 1-1-1, Tsukuba, 305-8571, Japan

    Norihisa Hoshino, Fumichika Iijima, Graham N. Newton, Norifumi Yoshida, Takuya Shiga & Hiroki Oshio

  2. Institute for Materials Research, Tohoku University, Katahira 2-1-1, Sendai, 980-8577, Japan

    Hiroyuki Nojiri

  3. Photon Factory and Condensed Matter Research Center, Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK), 1-1 Oho, Tsukuba, 305-0801, Ibaraki, Japan

    Akiko Nakao, Reiji Kumai & Youichi Murakami

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  1. Norihisa Hoshino
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Contributions

H.O. conceived and supervised the project. N.H., F.I. and N.Y. planned and implemented the synthetic and analytical experiments. G.N.N. finalized the X-ray data, helped with the analysis and wrote the manuscript. T.S. helped plan, implement and interpret the magnetic studies. H.N. performed conductivity and permittivity measurements. A.N., R.K. and Y.M. performed the synchrotron X-ray data collections.

Corresponding author

Correspondence to Hiroki Oshio.

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The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 3143 kb)

Supplementary information

Crystallographic data for LT1 phase, Mo Kalpha source (CIF 23 kb)

Supplementary information

Crystallographic data for LT1 phase, synchrotron source (CIF 23 kb)

Supplementary information

Crystallographic data for HT1 phase, Mo Kalpha source (CIF 26 kb)

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Crystallographic data for LT2 phase, Mo Kalpha source (CIF 23 kb)

Supplementary information

Crystallographic data for HT2 phase, Mo Kalpha source (CIF 25 kb)

Supplementary information

Crystallographic data for chiral chain (1), synchrotron source (CIF 24 kb)

Supplementary information

Crystallographic data for the product obtained with a racemic mixture of ligands, Mo Kalpha source (CIF 43 kb)

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Hoshino, N., Iijima, F., Newton, G. et al. Three-way switching in a cyanide-bridged [CoFe] chain. Nature Chem 4, 921–926 (2012). https://doi.org/10.1038/nchem.1455

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