Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Electron delocalization and charge mobility as a function of reduction in a metal–organic framework

Nature Materials volume 17, pages 625–632 (2018)Cite this article

Subjects

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.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Structural properties of K x Fe2(BDP)3.
Fig. 2: Experimental characterization of potassium insertion into Fe2(BDP)3.
Fig. 3: Mössbauer spectra and cyclic voltammogram of K x Fe2(BDP)3.
Fig. 4: Electronic structure calculations for the model system Fe(pz)3.
Fig. 5: Characterization of charge transport in K x Fe2(BDP)3.

Similar content being viewed by others

References

  1. Tian, Z.-R. et al. Manganese oxide mesoporous structures: mixed-valent semiconducting catalysts. Science 276, 926–930 (1997).

    Article  Google Scholar 

  2. Pandolfo, A. G. & Hollenkamp, A. F. Carbon properties and their role in supercapacitors. J. Power Sources 157, 11–27 (2006).

    Article  Google Scholar 

  3. Davis, M. E. Ordered porous materials for emerging applications. Nature 417, 813–821 (2002).

    Article  Google Scholar 

  4. Usman, M., Mendirata, S. & Lu, K.-L. Metal–organic frameworks: new interlayer dielectric materials. ChemElectroChem 2, 786–788 (2015).

    Article  Google Scholar 

  5. Long, J. R. & Yaghi, O. M. The pervasive chemistry of metal–organic frameworks. Chem. Soc. Rev. 38, 1213–1214 (2009).

    Article  Google Scholar 

  6. Sculley, J., Yang, D. & Zhou, H.-C. The current status of hydrogen storage in metal–organic frameworks, updated. Energy Environ. Sci. 4, 2721–2735 (2011).

    Article  Google Scholar 

  7. Eddaoudi, M. et al. Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage. Science 295, 469–472 (2002).

    Article  Google Scholar 

  8. Matsuda, R. et al. Highly controlled acetylene accommodation in a metal–organic microporous material. Nature 436, 238–241 (2005).

    Article  Google Scholar 

  9. Sun, L., Campbell, M. G. & Dincă, M. Electrically conductive porous metal–organic frameworks. Angew. Chem. Int. Ed. 55, 3566–3579 (2016).

    Article  Google Scholar 

  10. Givaja, G., Amo-Ochoa, P., Gómez-García, C. J. & Zamora, F. Electrical conductive coordination polymers. Chem. Soc. Rev. 41, 115–147 (2012).

  11. Huang, X. et al. A two-dimensional π–d conjugated coordination polymer with extremely high electrical conductivity and ambipolar transport behaviour. Nat. Commun. 6, 7480 (2015).

    Article  Google Scholar 

  12. D’Alessandro, D. M., Kanga, J. R. R. & Caddy, J. S. Towards conducting metal–organic frameworks. Aust. J. Chem. 64, 718–722 (2011).

    Article  Google Scholar 

  13. Darago, L. E., Aubrey, M. L., Yu, C. J., Gonzalez, M. I. & Long, J. R. Electronic conductivity, ferrimagnetic ordering, and reductive insertion mediated by organic mixed-valence in a ferric semiquinoid metal–organic framework. J. Am. Chem. Soc. 137, 15703–15711 (2015).

    Article  Google Scholar 

  14. D’Alessandro, D. M. Exploiting redox activity in metal–organic frameworks: concepts, trends and perspectives. Chem. Commun. 52, 8957–8971 (2016).

    Article  Google Scholar 

  15. Horike, S. et al. Fe2+-based layered porous coordination polymers and soft encapsulation of guests via redox activity. J. Mater. Chem. A 1, 3675–3679 (2013).

    Article  Google Scholar 

  16. Kobayashi, Y., Jacobs, B., Allendorf, M. D. & Long, J. R. Conductivity, doping, and redox chemistry of a microporous dithiolene-based metal–organic framework. Chem. Mater. 22, 4120–4122 (2010).

    Article  Google Scholar 

  17. Gándara, F. et al. Porous, conductive metal-triazolates and their structural elucidation by the charge-flipping method. Chem. Eur. J. 18, 10595–10601 (2012).

    Article  Google Scholar 

  18. Meilikhov, M. et al. Reduction of a metal–organic framework by an organometallic complex: magnetic properties and structure of the inclusion compound [(η5-C5H5)2Co]0.5@MIL-47(V). Angew. Chem. Int. Ed. 49, 6212–6215 (2010).

    Article  Google Scholar 

  19. Jacobson, A. J. & Nazar, L. F. in Encyclopedia of Inorganic and Bioinorganic Chemistry https://doi.org/10.1002/9781119951438.eibc0093 (Wiley, Medford, MA, 2006).

  20. Férey, G. et al. Mixed-valence Li/Fe-based metal–organic frameworks with both reversible redox and sorption properties. Angew. Chem. Int. Ed. 46, 3259–3263 (2007).

    Article  Google Scholar 

  21. Aubrey, M. L. & Long, J. R. A dual-ion battery cathode via oxidative insertion of anions in metal–organic framework. J. Am. Chem. Soc. 137, 13594–13602 (2015).

    Article  Google Scholar 

  22. Kung, C.-W. et al. Metal–organic framework thin films composed of free-standing acicular nanorods exhibiting reversible electrochromism. Chem. Mater. 25, 5012–5017 (2013).

    Article  Google Scholar 

  23. Creutz, C. Mixed valence complexes of d 5–d 6 metal centers. Prog. Inorg. Chem. 30, 1–73 (1983).

    Google Scholar 

  24. Herm, Z. R. et al. Separation of hexane isomers in a metal–organic framework with triangular channels. Science 340, 960–964 (2013).

    Article  Google Scholar 

  25. Feller, R. K. & Cheetham, A. K. Fe(III), Mn(II), Co(II), and Ni(II) 3,4,5-trihydroxybenzoate (gallate) dihydrates; a new family of hybrid framework materials. Solid State Sci. 8, 1121–1125 (2006).

    Article  Google Scholar 

  26. Sun, L., Hendon, C. H., Minier, M. A., Walsh, A. & Dincă, M. Million-fold electrical conductivity enhancement in Fe2(DEBDC) versus Mn2(DEBDC) (E = S, O). J. Am. Chem. Soc. 137, 6164–6167 (2015).

    Article  Google Scholar 

  27. Mason, J. A. et al. Methane storage in flexible metal–organic frameworks with intrinsic thermal management. Nature 527, 357–361 (2015).

    Article  Google Scholar 

  28. Torrance, J. B., Scott, B. A., Welber, B., Kauffman, F. B. & Seiden, P. E. Optical properties of the radical cation tetrathiafulvalenium (TTF+) in its mixed valence and monovalence halide salts. Phys. Rev. B 19, 730–741 (1979).

    Article  Google Scholar 

  29. Parthey, M. & Kaupp, M. Quantum-chemical insight into mixed-valence systems within and beyond the Robin-Day scheme. Chem. Soc. Rev. 43, 5067–5088 (2014).

    Article  Google Scholar 

  30. Collman, J. P. et al. Synthetic, electrochemical, optical, and conductivity studies of coordination polymers of iron, ruthenium, and osmium octaethylporphyrin. J. Am. Chem. Soc. 109, 4606–4614 (1987).

    Article  Google Scholar 

  31. Tanner, D. B., Jacobsen, C. S., Garito, A. F. & Heeger, A. J. Infrared studies of the energy gap in tetrathiofulvalene-tetracyanoquinodimethane (TTF-TCNQ). Phys. Rev. B 13, 3381–3404 (1976).

    Article  Google Scholar 

  32. Fincher, C. R. Jr., Ozaki, M., Heeger, A. J. & MacDiarmid, A. G. Donor and acceptor states in lightly doped polyacetylene, (CH) x . Phys. Rev. B 19, 4140–4148 (1979).

    Article  Google Scholar 

  33. Masciocchi, N. et al. One-dimensional polymers containing strictly collinear metal ions: synthesis and XRPD characterization of homoleptic binary metal pyrazolates. Inorg. Chem. 41, 6080–6089 (2002).

    Article  Google Scholar 

  34. Maxisch, T., Zhou, F. & Ceder, G. Ab initio study of the migration of small polarons in olivine Li x FePO4 and their association with lithium ions and vacancies. Phys. Rev. B 73, 104301 (2006).

    Article  Google Scholar 

  35. Alexandrov, V., Neumann, A., Scherer, M. M. & Rosso, K. M. Electron exchange and conduction in nontronite from first-principles. J. Phys. Chem. C 117, 2032–2040 (2013).

    Article  Google Scholar 

  36. Adelstein, N., Neaton, J. B., Asta, M. & De Jonghe, L. C. Density functional theory based calculation of small-polaron mobility in hematite. Phys. Rev. B 89, 245115-1 (2014).

    Article  Google Scholar 

  37. Narayan, T. C., Miyaki, T., Seki, S. & Dincă, M. High charge mobility in a tetrathiafulvalene-based metal–organic framework. J. Am. Chem. Soc. 134, 12933–12935 (2012).

    Google Scholar 

  38. Saeki, A., Koizumi, Y., Aida, T. & Seki, S. Comprehensive approach to intrinsic charge carrier mobility in conjugated organic molecules, macromolecules, and supramolecular architectures. Acc. Chem. Res. 45, 1193–1202 (2012).

    Article  Google Scholar 

  39. Saeki, A., Seki, S., Takenobu, T., Iwasa, Y. & Tagawa, S. Mobility and dynamics of charge carriers in rubrene single crystals studied by flash-photolysis microwave conductivity and optical spectroscopy. Adv. Mater. 20, 920–923 (2008).

    Article  Google Scholar 

  40. Krebs, F. C. & Jørgensen, M. High carrier mobility in a series of new semiconducting PPV-type polymers. Macromolecules 36, 4379–4384 (2003).

    Article  Google Scholar 

  41. Park, S. S. et al. Cation-dependent intrinsic electrical conductivity in isostructural tetrathiafulvalene-based microporous metal–organic frameworks. J. Am. Chem. Soc. 137, 1774–1777 (2015).

    Article  Google Scholar 

  42. Talin, A. A. et al. Tunable electrical conductivity in metal–organic framework thin-film devices. Science 343, 66–69 (2014).

    Article  Google Scholar 

  43. Sirringhaus, H. et al. Two-dimensional charge transport in self-organized, high-mobility conjugated polymers. Nature 401, 685–688 (1999).

    Article  Google Scholar 

  44. Kanicki, J., Libsch, F. R., Griffith, J. & Polastre, R. Performance of thin hydrogenated amorphous silicon thin-film transistors. J. Appl. Phys. 69, 2339–2345 (1991).

    Article  Google Scholar 

  45. Bright, A., Chaikin, P. M. & McGhie, A. R. Photoconductivity and small-polaron effects in tetracyanoquinodimethane. Phys. Rev. B 10, 3560–3568 (1974).

    Article  Google Scholar 

  46. Sheberla, D. et al. High electrical conductivity in Ni3(2,3,6,7,10,11-hexaminotriphenylene)2, a semiconducting metal–organic graphene analogue. J. Am. Chem. Soc. 136, 8859–8862 (2014).

    Article  Google Scholar 

  47. Wiers, B. M. Charge Transport in Metal-Organic Frameworks. PhD thesis, Univ. California Berkeley (2015).

  48. Coelho, A. Indexing of powder diffraction patterns by iterative use of singular value decomposition. Appl. Cryst. 36, 86–95 (2003).

    Article  Google Scholar 

  49. Cheary, R. W. & Coelho, A. A. Axial divergence in a conventional X-ray powder diffractometer. I. Theoretical foundations. J. Appl. Crystallogr. 31, 851–861 (1998).

    Article  Google Scholar 

  50. Coelho, A. TOPAS-Academic, v.4.1 (Coelho Software 2007).

  51. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

    Article  Google Scholar 

  52. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    Article  Google Scholar 

  53. Anisimov, V. I., Aryasetiawan, F. & Lichtenstein, A. I. First-principles calculations of the electronic structure and spectra of strongly correlated systems: the LDA + U method. J. Phys. Condens. Matter 9, 767–808 (1997).

    Article  Google Scholar 

  54. Dudarev, S. L., Botton, G. A., Savrasov, S. Y., Humphreys, C. J. & Sutton, A. P. Electron-energy-loss spectra and the structural stability of nickel oxide: an LSDA + U study. Phys. Rev. B 57, 1505–1509 (1998).

    Article  Google Scholar 

  55. Krukau, A. V., Vydrov, O. A., Izmaylov, A. F. & Scuseria, G. E. Influence of the exchange screening parameter on the performance of screened hybrid functionals. J. Chem. Phys. 125, 224106 (2006).

    Article  Google Scholar 

Download references

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

  1. Sean C. Andrews

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

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

Authors and 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

Authors
  1. Michael L. Aubrey
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Brian M. Wiers
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Sean C. Andrews
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Tsuneaki Sakurai
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Sebastian E. Reyes-Lillo
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Samia M. Hamed
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Chung-Jui Yu
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Lucy E. Darago
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Jarad A. Mason
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Jin-Ook Baeg
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Fernande Grandjean
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Gary J. Long
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Shu Seki
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Jeffrey B. Neaton
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. Peidong Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  16. Jeffrey R. Long
    View author publications

    You can also search for this author in PubMed Google Scholar

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.

Corresponding authors

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

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

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

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Aubrey, M.L., Wiers, B.M., Andrews, S.C. et al. Electron delocalization and charge mobility as a function of reduction in a metal–organic framework. Nature Mater 17, 625–632 (2018). https://doi.org/10.1038/s41563-018-0098-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

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

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing