Atomically precise single-crystal structures of electrically conducting 2D metal–organic frameworks


Electrically conducting 2D metal–organic frameworks (MOFs) have attracted considerable interest, as their hexagonal 2D lattices mimic graphite and other 2D van der Waals stacked materials. However, understanding their intrinsic properties remains a challenge because their crystals are too small or of too poor quality for crystal structure determination. Here, we report atomically precise structures of a family of 2D π-conjugated MOFs derived from large single crystals of sizes up to 200 μm, allowing atomic-resolution analysis by a battery of high-resolution diffraction techniques. A designed ligand core rebalances the in-plane and out-of-plane interactions that define anisotropic crystal growth. We report two crystal structure types exhibiting analogous 2D honeycomb-like sheets but distinct packing modes and pore contents. Single-crystal electrical transport measurements distinctively demonstrate anisotropic transport normal and parallel to the π-conjugated sheets, revealing a clear correlation between absolute conductivity and the nature of the metal cation and 2D sheet packing motif.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Fig. 1: Design strategy and synthetic conditions for the growth of single crystals of 2D MOFs.
Fig. 2: Single-crystal structure of Cu3HHTT2 derived from cRED and HRTEM.
Fig. 3: Single-crystal structure of Co6HHTT3 derived from SXRD and HRTEM.
Fig. 4: Electrical transport data for 2D MmHHTTn MOFs.

Data availability

The crystallographic information has been deposited in the Cambridge Crystallographic Data Centre (CCDC) under accession codes 20318522031856. All other data supporting the findings of this study are available within the article and its Supplementary Information.


  1. 1.

    Hmadeh, M. et al. New porous crystals of extended metal-catecholates. Chem. Mater. 24, 3511–3513 (2012).

    CAS  Google Scholar 

  2. 2.

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

    CAS  Google Scholar 

  3. 3.

    Dong, R. et al. High-mobility band-like charge transport in a semiconducting two-dimensional metal–organic framework. Nat. Mater. 17, 1027–1032 (2018).

    CAS  Google Scholar 

  4. 4.

    Kambe, T. et al. π-Conjugated nickel bis(dithiolene) complex nanosheet. J. Am. Chem. Soc. 135, 2462–2465 (2013).

    CAS  Google Scholar 

  5. 5.

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

    CAS  Google Scholar 

  6. 6.

    Aubrey, M. L. et al. Electron delocalization and charge mobility as a function of reduction in a metal–organic framework. Nat. Mater. 17, 625–632 (2018).

    CAS  Google Scholar 

  7. 7.

    Nam, K. W. et al. Conductive 2D metal-organic framework for high-performance cathodes in aqueous rechargeable zinc batteries. Nat. Commun. 10, 4948 (2019).

    Google Scholar 

  8. 8.

    Wada, K., Sakaushi, K., Sasaki, S. & Nishihara, H. Multielectron-transfer-based rechargeable energy storage of two-dimensional coordination frameworks with non-innocent ligands. Angew. Chem. Int. Ed. 57, 8886–8890 (2018).

    CAS  Google Scholar 

  9. 9.

    Pomerantseva, E., Bonaccorso, F., Feng, X., Cui, Y. & Gogotsi, Y. Energy storage: the future enabled by nanomaterials. Science 366, eaan8285 (2019).

    CAS  Google Scholar 

  10. 10.

    Sheberla, D. et al. Conductive MOF electrodes for stable supercapacitors with high areal capacitance. Nat. Mater. 16, 220–224 (2017).

    CAS  Google Scholar 

  11. 11.

    Wang, H., Zhu, Q.-L., Zou, R. & Xu, Q. Metal-organic frameworks for energy applications. Chem 2, 52–80 (2017).

    CAS  Google Scholar 

  12. 12.

    Feng, D. et al. Robust and conductive two-dimensional metal–organic frameworks with exceptionally high volumetric and areal capacitance. Nat. Energy 3, 30–36 (2018).

    CAS  Google Scholar 

  13. 13.

    Miner, E. M. et al. Electrochemical oxygen reduction catalysed by Ni3(hexaiminotriphenylene)2. Nat. Commun. 7, 10942 (2016).

    CAS  Google Scholar 

  14. 14.

    Stassen, I. et al. An updated roadmap for the integration of metal–organic frameworks with electronic devices and chemical sensors. Chem. Soc. Rev. 46, 3185–3241 (2017).

    CAS  Google Scholar 

  15. 15.

    Evans, A. M. et al. Seeded growth of single-crystal two-dimensional covalent organic frameworks. Science 361, 52–57 (2018).

    CAS  Google Scholar 

  16. 16.

    Ma, T. et al. Single-crystal X-ray diffraction structures of covalent organic frameworks. Science 361, 48–52 (2018).

    CAS  Google Scholar 

  17. 17.

    Zhao, M. et al. Two-dimensional metal–organic framework nanosheets: synthesis and applications. Chem. Soc. Rev. 47, 6267–6295 (2018).

    CAS  Google Scholar 

  18. 18.

    Zhong, Y. et al. Wafer-scale synthesis of monolayer two-dimensional porphyrin polymers for hybrid superlattices. Science 9385, 1379–1384 (2019).

    Google Scholar 

  19. 19.

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

    CAS  Google Scholar 

  20. 20.

    Dou, J.-H. et al. Signature of metallic behavior in the metal–organic frameworks M3(hexaiminobenzene)2 (M = Ni, Cu). J. Am. Chem. Soc. 139, 13608–13611 (2017).

    CAS  Google Scholar 

  21. 21.

    Day, R. W. et al. Single crystals of electrically conductive two-dimensional metal–organic frameworks: structural and electrical transport properties. ACS Cent. Sci. 5, 1959–1964 (2019).

    CAS  Google Scholar 

  22. 22.

    Miao, Q. Ten years of N-heteropentacenes as semiconductors for organic thin-film transistors. Adv. Mater. 26, 5541–5549 (2014).

    CAS  Google Scholar 

  23. 23.

    Wang, C., Dong, H., Jiang, L. & Hu, W. Organic semiconductor crystals. Chem. Soc. Rev. 47, 422–500 (2018).

    CAS  Google Scholar 

  24. 24.

    Watson, M. D., Fechtenkötter, A. & Müllen, K. Big is beautiful - ‘Aromaticity’ revisited from the viewpoint of macromolecular and supramolecular benzene chemistry. Chem. Rev. 101, 1267–1300 (2001).

    CAS  Google Scholar 

  25. 25.

    Okamoto, T. et al. Robust, high-performance n-type organic semiconductors. Sci. Adv. 6, eaaz0632 (2020).

    CAS  Google Scholar 

  26. 26.

    Rieth, A. J., Wright, A. M. & Dincă, M. Kinetic stability of metal–organic frameworks for corrosive and coordinating gas capture. Nat. Rev. Mater. 4, 708–725 (2019).

    CAS  Google Scholar 

  27. 27.

    Van Vleet, M. J., Weng, T., Li, X. & Schmidt, J. R. In situ, time-resolved, and mechanistic studies of metal–organic framework nucleation and growth. Chem. Rev. 118, 3681–3721 (2018).

    Google Scholar 

  28. 28.

    Skorupskii, G. et al. Efficient and tunable one-dimensional charge transport in layered lanthanide metal–organic frameworks. Nat. Chem. 12, 131–136 (2020).

    CAS  Google Scholar 

  29. 29.

    Zhang, D. et al. Atomic-resolution transmission electron microscopy of electron beam-sensitive crystalline materials. Science 359, 675–679 (2018).

    CAS  Google Scholar 

  30. 30.

    Liu, K. et al. On-water surface synthesis of crystalline, few-layer two-dimensional polymers assisted by surfactant monolayers. Nat. Chem. 11, 994–1000 (2019).

    CAS  Google Scholar 

  31. 31.

    Lebedev, O. I., Millange, F., Serre, C., Van Tendeloo, G. & Férey, G. First direct imaging of giant pores of the metal–organic framework MIL-101. Chem. Mater. 17, 6525–6527 (2005).

    CAS  Google Scholar 

  32. 32.

    Wiktor, C., Meledina, M., Turner, S., Lebedev, O. I. & Fischer, R. A. Transmission electron microscopy on metal–organic frameworks - a review. J. Mater. Chem. A 5, 14969–14989 (2017).

    CAS  Google Scholar 

  33. 33.

    Liu, L. et al. Imaging defects and their evolution in a metal–organic framework at sub-unit-cell resolution. Nat. Chem. 11, 622–628 (2019).

    CAS  Google Scholar 

  34. 34.

    Li, Y. et al. Cryo-EM structures of atomic surfaces and host-guest chemistry in metal-organic frameworks. Matter 1, 428–438 (2019).

    Google Scholar 

  35. 35.

    Mayoral, A., Mahugo, R., Sánchez-Sánchez, M. & Díaz, I. Cs-corrected STEM imaging of both pure and silver-supported metal-organic framework MIL-100(Fe). ChemCatChem 9, 3497–3502 (2017).

    CAS  Google Scholar 

  36. 36.

    Shen, B., Chen, X., Shen, K., Xiong, H. & Wei, F. Imaging the node-linker coordination in the bulk and local structures of metal-organic frameworks. Nat. Commun. 11, 2692 (2020).

    CAS  Google Scholar 

  37. 37.

    Zhou, Y. et al. Local structure evolvement in MOF single crystals unveiled by scanning transmission electron microscopy. Chem. Mater. 32, 4966–4972 (2020).

    CAS  Google Scholar 

  38. 38.

    Cao, Y. et al. Unconventional superconductivity in magic-angle graphene superlattices. Nature 556, 43–50 (2018).

    CAS  Google Scholar 

  39. 39.

    Hestand, N. J. & Spano, F. C. Expanded theory of H- and J-molecular aggregates: the effects of vibronic coupling and intermolecular charge transfer. Chem. Rev. 118, 7069–7163 (2018).

    CAS  Google Scholar 

  40. 40.

    Xie, L. S., Skorupskii, G. & Dincǎ, M. Electrically conductive metal–organic frameworks. Chem. Rev. 120, 8536–8580 (2020).

    CAS  Google Scholar 

  41. 41.

    Sheldrick, G. M. SHELXT - Integrated space-group and crystal-structure determination. Acta Crystallogr. Sect. A Found. Crystallogr. 71, 3–8 (2015).

    Google Scholar 

  42. 42.

    Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta Crystallogr. Sect. C. Struct. Chem. 71, 3–8 (2015).

    Google Scholar 

  43. 43.

    Spek, A. L. PLATON SQUEEZE: a tool for the calculation of the disordered solvent contribution to the calculated structure factors. Acta Crystallogr. Sect. C. Struct. Chem. 71, 9–18 (2015).

    CAS  Google Scholar 

  44. 44.

    Wang, Y. et al. Elucidation of the elusive structure and formula of the active pharmaceutical ingredient bismuth subgallate by continuous rotation electron diffraction. Chem. Commun. 53, 7018–7021 (2017).

    CAS  Google Scholar 

  45. 45.

    Smeets, S., Zou, X. & Wan, W. Serial electron crystallography for structure determination and phase analysis of nanocrystalline materials. J. Appl. Crystallogr. 51, 1262–1273 (2018).

    CAS  Google Scholar 

  46. 46.

    Wan, W., Sun, J., Su, J., Hovmöller, S. & Zou, X. Three-dimensional rotation electron diffraction: software RED for automated data collection and data processing. J. Appl. Crystallogr. 46, 1863–1873 (2013).

    CAS  Google Scholar 

  47. 47.

    Kabsch, W. et al. XDS. Acta Crystallogr. Sect. D. Biol. Crystallogr. 66, 125–132 (2010).

    CAS  Google Scholar 

  48. 48.

    Sun, L., Park, S. S., Sheberla, D. & Dincă, M. Measuring and reporting electrical conductivity in metal–organic frameworks: Cd2(TTFTB) as a case study. J. Am. Chem. Soc. 138, 14772–14782 (2016).

    CAS  Google Scholar 

Download references


This work was supported by the Army Research Office (grant number W911NF-17-1-0174). J.S. thanks National Natural Science Foundation of China (grant number 21527803,21621061) and Ministry of Science and Technology of China (grant number 2016YFA0301004). The staff of beamlines BL17B1 and BL19U1 of the National Facility for Protein Science Shanghai (NFPS) at the Shanghai Synchrotron Radiation Facility (SSRF) are acknowledged for their assistance in the data collection. Aberration-corrected TEM was carried out at the Center for Functional Nanomaterials (CFN), Brookhaven National Laboratory (BNL), which is supported by the US Department of Energy. Cryo-EM was carried out at the Automated Cryogenic Electron Microscopy Facility in MIT.nano. Use of the Advanced Photon Source (APS) at Argonne National Laboratory (ANL) and ANL’s contribution were supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. MRCAT operations, beamline 10-BM, are supported by the Department of Energy and the MRCAT member institutions. Part of the characterization and device fabrication was performed at the Harvard Center for Nanoscale Systems (CNS), a member of the National Nanotechnology Infrastructure Network (NNIN), which is supported by the National Science Foundation under NSF award no. ECS-0335765. Computational work was performed in the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the NSF (ACI-105357), and was supported by the Division of Materials Research under grant no. DMR-1956403. Y.L. thanks the Swedish Research Council and the Knut and Alice Wallenberg Foundation (KAW). J.-H.D. thanks W. S. Leong, R. W. Day and D. Zakharov for their assistance with electron-beam device fabrication and HRTEM data collection.

Author information




J.-H.D., J.S. and M.D. conceived the idea and designed the experiments. J.-H.D. performed and interpreted the synthesis, crystal growth, HRTEM (cryo-EM) experiments and electron-beam device fabrication. M.Q.A. performed and interpreted the AFM and device measurements. Y.L., J.L. and W.Z. carried out the crystallographic studies. J.L.M., M.C.Y. and C.H.H. performed and interpreted the pKa and DFT calculations. N.J.L. and J.T.M. performed and interpreted the XANES measurement. L.S., L.Y., T.C., G.S. and C.S. performed and interpreted the SEM, XPS, EPR and PXRD measurements. L.R.P., P.V.D. and E.J.B. helped with the HRTEM data processing. J.K. helped with the electron-beam device fabrication. All authors interpreted the results and wrote the manuscript.

Corresponding authors

Correspondence to Junliang Sun or Mircea Dincă.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Peer review information Nature Materials thanks Albert Talin and the other anonymous reviewers for their contribution to the peer review of this work.

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

Supplementary information

Supplementary Information

Supplementary Figs. 1–72, discussion, Tables 1–3 and refs. 1–35.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Dou, JH., Arguilla, M.Q., Luo, Y. et al. Atomically precise single-crystal structures of electrically conducting 2D metal–organic frameworks. Nat. Mater. (2020).

Download citation

Further reading


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