Abstract

Conductive metal–organic frameworks are an emerging class of three-dimensional architectures with degrees of modularity, synthetic flexibility and structural predictability that are unprecedented in other porous materials. However, engendering long-range charge delocalization and establishing synthetic strategies that are broadly applicable to the diverse range of structures encountered for this class of materials remain challenging. Here, we report the synthesis of K x Fe2(BDP)3 (0 ≤ x ≤ 2; BDP2− = 1,4-benzenedipyrazolate), which exhibits full charge delocalization within the parent framework and charge mobilities comparable to technologically relevant polymers and ceramics. Through a battery of spectroscopic methods, computational techniques and single-microcrystal field-effect transistor measurements, we demonstrate that fractional reduction of Fe2(BDP)3 results in a metal–organic framework that displays a nearly 10,000-fold enhancement in conductivity along a single crystallographic axis. The attainment of such properties in a K x Fe2(BDP)3 field-effect transistor represents the realization of a general synthetic strategy for the creation of new porous conductor-based devices.

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Acknowledgements

Synthesis and characterization of the bulk materials was supported by the National Science Foundation through grant DMR-1611525. Additional efforts to synthesize the materials in nanocrystalline form were funded by a grant from the Go KRICT Project for Future Technology of the Korea Research Institute of Chemical Technology (KRICT). We thank G. Halder for assisting with powder diffraction experiments, which were collected at Beamline 17-BM-B at the Advanced Photon Source, a DoE Office of Science User Facility operated by Argonne National Laboratory under contract no. DE-AC02-06CH11357. S.E.R.-L. and S.M.H. thank R. F. Berger and K. Lee for valuable discussions. Theory and computation were supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences (Theory FWP) Materials Sciences and Engineering Division (DE-AC02-05CH11231). Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract no. DE-AC02-05CH11231. Portions of the computation work were performed at the Molecular Graphics Facility at the Department of Chemistry of UC Berkeley. Support for FP-TRMC measurements conducted by S.S. and T.S. was funded by Japan Society for the Promotion of Science (JSPS) grant no. 15K21721. The FET part was supported by the US Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division under contract no. DE-AC02-05CH11231 (PChem KC3103). We further thank Arkema for fellowship support of M.L.A., the NSF GRFP for fellowship support of L.E.D and J.A.M., and K. R. Meihaus for editing assistance.

Author information

Author notes

    • Sean C. Andrews

    Present address: Corporate Research & Development, Qualcomm Technology Inc, San Diego, CA, USA

  1. These author contributed equally: Michael L. Aubrey, Brian M. Wiers, Sean C. Andrews.

Affiliations

  1. Department of Chemistry, University of California, Berkeley, CA, USA

    • Michael L. Aubrey
    • , Brian M. Wiers
    • , Sean C. Andrews
    • , Samia M. Hamed
    • , Chung-Jui Yu
    • , Lucy E. Darago
    • , Jarad A. Mason
    • , Peidong Yang
    •  & Jeffrey R. Long
  2. Department of Molecular Engineering, Kyoto University, Kyoto, Japan

    • Tsuneaki Sakurai
    •  & Shu Seki
  3. Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    • Sebastian E. Reyes-Lillo
    • , Samia M. Hamed
    •  & Jeffrey B. Neaton
  4. Department of Physics, University of California, Berkeley, CA, USA

    • Sebastian E. Reyes-Lillo
    • , Samia M. Hamed
    •  & Jeffrey B. Neaton
  5. Departamento de Ciencias Fisicas, Universidad Andres Bello, Santiago, Chile

    • Sebastian E. Reyes-Lillo
  6. Kavli Energy NanoSciences Institute at Berkeley, Berkeley, CA, USA

    • Samia M. Hamed
    • , Jeffrey B. Neaton
    •  & Peidong Yang
  7. Division of Green Chemistry and Engineering Research, Korea Research Institute of Chemical Technology, Daejeon, Republic of Korea

    • Jin-Ook Baeg
  8. Department of Chemistry, Missouri University of Science and Technology, University of Missouri, Rolla, MO, USA

    • Fernande Grandjean
    •  & Gary J. Long
  9. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    • Peidong Yang
    •  & Jeffrey R. Long
  10. Department of Materials Science and Engineering, University of California, Berkeley, CA, USA

    • Peidong Yang
  11. Department of Chemical and Biomolecular Engineering, University of California, Berkeley, CA, USA

    • Jeffrey R. Long

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Contributions

M.L.A. developed the electrochemical experiments, helped to determine the electronic structure and transport mechanism, coordinated the collaboration and wrote the manuscript. B.M.W., S.C.A., P.Y. and J.R.L. conceived of the idea and designed the study, B.M.W. synthesized and collected spectroscopic measurements, determined surface areas and coordinated the collaboration. S.C.A. fabricated and measured the FET devices, T.S. and S.S. conducted the FP-TRMC measurements, S.E.R.-L., S.M.H. and J.B.N. completed the theoretical computations, C.-J.Y conducted the electrochemical measurements, L.E.D. conducted the magnetic susceptibility measurements and helped determined the magnetic structure of the material, J.A.M. conducted the X-ray diffraction measurements, J.-O.B. helped conceive of the idea, and elucidate the transport mechanism, F.G. and G.J.L modelled the Mössbauer spectra, and determined the magnetic and electronic structure of the material. G.J.L, P.Y. and J.R.L. supervised and guided the project. All authors helped write the manuscript.

Competing interests

The authors declare no competing interests.

Corresponding authors

Correspondence to Gary J. Long or Peidong Yang or Jeffrey R. Long.

Supplementary information

  1. Supplementary Information

    Supplementary Discussion, Supplementary Figures 1–34, Supplementary Tables 1–7, Supplementary References 1–60

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DOI

https://doi.org/10.1038/s41563-018-0098-1

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