Article | Published:

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

Nature Chemistry volume 3, pages 949953 (2011) | Download Citation

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.

  • Compound C30H22N2O4Pd2

    Bis-(μ-acetato-O:O')-bis-[benzo[h]quinolinyl-N]dipalladium

  • Compound C30H22Cl2N2O4Pd2

    Bis-(μ-acetato-O:O')-bis-[benzo[h]quinolinyl-N]-bis-chlorodipalladium

  • Compound C30H22F2N2O4Pd2

    Bis-(μ-acetato-O:O')-bis-[benzo[h]quinolinyl-N]-bis-fluorodipalladium

  • Compound C13H8ClN

    10-Chlorobenzo[h]quinoline

  • Compound C38H38N2O4Pd2

    Bis-(μ-hexanoato-O:O')-bis-[benzo[h]quinolinyl-N]dipalladium

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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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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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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.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Tobias Ritter.

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Crystallographic information files

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    Crystallographic data for compound 3

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    Crystallographic data for compound 5

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    Crystallographic data for compound 8 at 100 K

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    Crystallographic data for compound 8 at 130 K

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    Crystallographic data for compound 8 at 160 K

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    Crystallographic data for compound 8 at 190 K

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    Crystallographic data for compound 8 at 220 K

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    Crystallographic data for compound 8 at 250 K

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DOI

https://doi.org/10.1038/nchem.1197

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