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Efficient and tunable one-dimensional charge transport in layered lanthanide metal–organic frameworks

Nature Chemistry volume 12, pages 131–136 (2020)Cite this article

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Abstract

The emergence of electrically conductive metal–organic frameworks (MOFs) has led to applications in chemical sensing and electrical energy storage, among others. The most conductive MOFs are made from organic ligands and square-planar transition metal ions connected into two-dimensional (2D) sheets stacked on top of each other. Their electrical properties are thought to depend critically on the covalency of the metal–ligand bond, and less importance is given to out-of-plane charge transport. Here, we report a series of lanthanide-based MOFs that allow fine tuning of the sheet stacking. In these materials, the Ln3+ ions lie between the planes of the ligands, thus connecting organic layers into a 3D framework through lanthanide–oxygen chains. Here, efficient charge transport is found to occur primarily perpendicular to the 2D sheets. These results demonstrate that high conductivity in layered MOFs does not necessarily require a metal–ligand bond with highly covalent character, and that interactions between organic ligands alone can produce efficient charge transport pathways.

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Fig. 1: Structure of NdHHTP.
Fig. 2: Electronic band structure and DOS of LaHHTP.
Fig. 3: Diffuse reflectance spectra for LnHHTP (Ln = La, Nd, Ho and Yb).
Fig. 4: Electrical conductivity of LnHHTP (Ln = Yb, Ho, Nd and La).

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Data availability

Crystallographic information obtained by Rietveld refinement of PXRD data has been deposited in the Cambridge Crystallographic Data Centre under accession codes CCDC 1874834 (NdHHTP) and CCDC 1874835 (YbHHTP). All other data supporting the findings of this study are available within the article and its Supplementary Information, or from the corresponding author upon reasonable request.

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Acknowledgements

This work was supported by the Army Research Office (grant no. W911NF-17-1-0174). Computational work used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the NSF (ACI-1053575). This research used resources of the Advanced Photon Source, a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. This work was performed in part at the Center for Nanoscale Systems (CNS), a member of the National Nanotechnology Coordinated Infrastructure Network, which is supported by the National Science Foundation under NSF award no. 1541959. CNS is part of Harvard University. We thank the staff of 17-BM for help with synchrotron X-ray data collectio, R.W. Day and L. Sun for assistance with SEM, T. Chen for assistance with NMR spectroscopy and I. Stassen, M.Q. Arguilla and L.S. Xie for helpful discussions.

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Authors and Affiliations

  1. Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA

    Grigorii Skorupskii & Mircea Dincă

  2. Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, MD, USA

    Benjamin A. Trump & Craig M. Brown

  3. Materials Science Institute, Department of Chemistry and Biochemistry, University of Oregon, Eugene, OR, USA

    Thomas W. Kasel & Christopher H. Hendon

  4. Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE, USA

    Craig M. Brown

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  1. Grigorii Skorupskii
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Contributions

G.S. and M.D. planned and designed the experiments. G.S. executed the syntheses, chemical, spectroscopic and electrical characterization. G.S., B.A.T. and C.M.B. collected and analysed the PXRD data. T.W.K. and C.H.H. performed the DFT studies. All authors were involved in the writing of the manuscript and have given consent to this publication.

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Correspondence to Mircea Dincă.

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Supplementary information

Supplementary Information

Additional synthesis and characterization data, Supplementary Tables 1–2, Figs. 1–48 and refs. 1–21.

Crystallographic data

CIF for NdHHTP; CCDC reference 1874834.

Crystallographic data

CIF for YbHHTP; CCDC reference 1874835.

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Skorupskii, G., Trump, B.A., Kasel, T.W. et al. Efficient and tunable one-dimensional charge transport in layered lanthanide metal–organic frameworks. Nat. Chem. 12, 131–136 (2020). https://doi.org/10.1038/s41557-019-0372-0

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