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

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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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          Most cited references35

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          Efficient iterative schemes forab initiototal-energy calculations using a plane-wave basis set

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            Conductive MOF electrodes for stable supercapacitors with high areal capacitance

            Using MOFs as active electrodes in electrochemical double layer capacitors has so far proved difficult. An electrically conductive MOF used as an electrode is now shown to exhibit electrochemical performance similar to most carbon-based materials.
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              High electrical conductivity in Ni₃(2,3,6,7,10,11-hexaiminotriphenylene)₂, a semiconducting metal-organic graphene analogue.

              Reaction of 2,3,6,7,10,11-hexaaminotriphenylene with Ni(2+) in aqueous NH3 solution under aerobic conditions produces Ni3(HITP)2 (HITP = 2,3,6,7,10,11-hexaiminotriphenylene), a new two-dimensional metal-organic framework (MOF). The new material can be isolated as a highly conductive black powder or dark blue-violet films. Two-probe and van der Pauw electrical measurements reveal bulk (pellet) and surface (film) conductivity values of 2 and 40 S·cm(-1), respectively, both records for MOFs and among the best for any coordination polymer.
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                Author and article information

                Journal
                Nat Chem
                Nature chemistry
                Springer Science and Business Media LLC
                1755-4349
                1755-4330
                February 2020
                : 12
                : 2
                Affiliations
                [1 ] Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA.
                [2 ] Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, MD, USA.
                [3 ] Materials Science Institute, Department of Chemistry and Biochemistry, University of Oregon, Eugene, OR, USA.
                [4 ] Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE, USA.
                [5 ] Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA. mdinca@mit.edu.
                Article
                10.1038/s41557-019-0372-0
                10.1038/s41557-019-0372-0
                31767997
                dad94da4-7ce2-4d6c-bba1-fa0cb7ff1c35
                History

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