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A molecular metal with ion-conducting channels

Nature volume 394, pages 159–162 (1998)Cite this article

Abstract

Metallic behaviour is well known in charge-transfer complexes that contain stacks of planar, partially oxidized (or reduced) π-conjugated molecules. Electronic conduction occurs in the partially occupied, delocalized π bands formed by intermolecular orbital overlap, and some of these materials exhibit superconductivity1,2. Counter-ions, present to achieve charge neutrality, usually play a passive role, although in some cases they couple to the electronic structure, for example by imposing a new structural periodicity (a superlattice) by orientational ordering1. The development of molecular solids that can simultaneously support the transport of both electrons and ions is important for several fields, including the development of solid-state batteries3,4, electroluminescent devices5 and biomimetic systems6,7. Crown ethers are promising components for such systems, as they provide cavities through which ion motion might occur. Here we report that the charge-transfer salt Li0.6(15-crown-5-ether)[Ni(dmit)2]2·H2O exhibits both electron and ion conductivity: the stacks of the nickel complex (dmit is an organic molecule) provide a pathway for electron conduction, and stacks of the crown ethers provide channels for lithium-ion motion. Evidence for the latter above 250 K is provided by NMR and conductivity studies. We also see evidence for coupling of the electron and ion motions. This compound might serve as a model for the development of other hybrid electronic/ionic conducting materials.

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Figure 1: Structure and packing of the 15-crown-5-ether and Ni(dmit)2.
Figure 2: Temperature dependence of electrical resistance of a crystal of Li0.6 (15-crown-5-ether) [Ni(dmit)2]2·H2O.
Figure 3: Magnetic susceptibility versus temperature for Li0.6 (15-crown-5-ether) [Ni(dmit)2]2·H2.
Figure 4: Temperature dependence of the linewidth of cross-polarization magic-angle-spinning NMR spectra for 7Li in crystals of Li0.6 (15-crown-5-ether) [Ni(dmit)2]2·H2O.

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Acknowledgements

We thank N. Robertson for synthesis of some of the crystals used in this work, N.Nonose for measurements of the ICP mass spectra, and A. Yap and S. R. Elliott for assistance with the NMR measurements. This work was supported by Grant-in-aid for Science Research from the Ministry of Education, Science and Culture, Japan, and the UK Engineering and Physical Sciences Research Council. One of the authors (A.E.U.) acknowledges support from the British Council.

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Authors and Affiliations

  1. Research Institute for Electronic Science, Hokkaido University, 060, Sapporo, Japan

    Takayoshi Nakamura & Tomoyuki Akutagawa

  2. National Institute for Materials and Chemical Research, Tsukuba, 305, Ibaraki, Japan

    Kazumasa Honda

  3. Department of Chemistry, University College of North Wales, Bangor, LL57 2UW, Gwynedd, UK

    Allan E. Underhill

  4. Cavendish Laboratory, University of Cambridge, Madingley Road, CB3 0HE, Cambridge, UK

    A. Treeve Coomber & Richard H. Friend

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  1. Takayoshi Nakamura
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Correspondence to Richard H. Friend.

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Nakamura, T., Akutagawa, T., Honda, K. et al. A molecular metal with ion-conducting channels. Nature 394, 159–162 (1998). https://doi.org/10.1038/28128

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