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Synthesis and structure of solution-stable one-dimensional palladium wires

Nature Chemistry volume 3, pages 949–953 (2011)Cite this article

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Abstract

One-dimensional metal wires are valuable materials because of their optical and electronic anisotropy, and they have potential utility in devices such as photovoltaic cells and molecular sensors. However, despite more than a century of research, only a few examples exist of well-defined one-dimensional (1D) metal wires that allow for the rational variation of conductivity. Herein we describe the first examples of 1D molecular wires supported by Pd–Pd bonds, the thin-film conductive properties of which can be altered by controlled molecular changes. Wires based on Pd(III) give semiconducting films with a modifiable bandgap, whereas wires based on Pd(2.5) give films that display metallic conductivity above 200 K: a metallic state has not been reported previously for any polymer composed of 1D metal wires. The wires are infinite in the solid state and maintain 1D structures in solution with lengths of up to 750 nm. Solution stability enables thin film coating, a requisite for device fabrication using molecular wires.

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Figure 1: Synthesis of a Pd(III) wire with Pd–Pd bonds.
Figure 2: X-ray crystal structure of 1D Pd(III) wire 5.
Figure 3: UV-vis/NIR absorption spectra of Pd(III) wires.
Figure 4: Temperature-dependent thin-film conductivity of 1D palladium wires 5 and 8.

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Acknowledgements

We thank T.A. Betley, A. Cohen and D.G. Nocera for discussions, S-L. Zheng and P. Müller for X-ray crystallographic analysis, T. Cook for help with NIR spectroscopy, R.A. Cabanas, S. Fraden and C. Schatz for assistance with light scattering, the Air Force Office of Scientific Research (FA9550-10-1-0170) and National Science Foundation (CHE-0952753) for funding and the Department of Energy Office of Science Graduate Fellowship for a graduate fellowship for M.G.C.

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Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts, USA

    Michael G. Campbell, David C. Powers, Jean Raynaud, Michael J. Graham, Ping Xie, Eunsung Lee & Tobias Ritter

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  1. Michael G. Campbell
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Contributions

M.G.C., D.C.P., J.R. and T.R. conceived and designed the experiments, M.G.C., D.C.P., J.R., M.J.G. and P.X. performed the experiments, M.G.C. and E.L. carried out the theoretical calculations and M.G.C., D.C.P., J.R. and T.R. co-wrote the paper.

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Correspondence to Tobias Ritter.

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The authors declare no competing financial interests.

Supplementary information

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Supplementary information (PDF 9506 kb)

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Crystallographic data for compound 3 (CIF 25 kb)

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Crystallographic data for compound 5 (CIF 25 kb)

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Crystallographic data for compound 8 at 100 K (CIF 27 kb)

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Crystallographic data for compound 8 at 130 K (CIF 26 kb)

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Crystallographic data for compound 8 at 160 K (CIF 26 kb)

Supplementary information

Crystallographic data for compound 8 at 190 K (CIF 26 kb)

Supplementary information

Crystallographic data for compound 8 at 220 K (CIF 26 kb)

Supplementary information

Crystallographic data for compound 8 at 250 K (CIF 27 kb)

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Campbell, M., Powers, D., Raynaud, J. et al. Synthesis and structure of solution-stable one-dimensional palladium wires. Nature Chem 3, 949–953 (2011). https://doi.org/10.1038/nchem.1197

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