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      Single Crystals of Electrically Conductive Two-Dimensional Metal–Organic Frameworks: Structural and Electrical Transport Properties

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          Abstract

          Crystalline, electrically conductive, and intrinsically porous materials are rare. Layered two-dimensional (2D) metal–organic frameworks (MOFs) break this trend. They are porous crystals that exhibit high electrical conductivity and are novel platforms for studying fundamentals of electricity and magnetism in two dimensions. Despite demonstrated applications, electrical transport in these remains poorly understood because of a lack of single crystal studies. Here, studies of single crystals of two 2D MOFs, Ni 3(HITP) 2 and Cu 3(HHTP) 2, uncover critical insights into their structure and transport. Conductivity measurements down to 0.3 K suggest metallicity for mesoscopic single crystals of Ni 3(HITP) 2, which contrasts with apparent activated conductivity for polycrystalline films. Microscopy studies further reveal that these MOFs are not isostructural as previously reported. Notably, single rods exhibit conductivities up to 150 S/cm, which persist even after prolonged exposure to ambient conditions. These single crystal studies confirm that 2D MOFs hold promise as molecularly tunable platforms for fundamental science and applications where porosity and conductivity are critical.

          Abstract

          A single crystal conductive metal−organic frameworks device and its metallic conduction.

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          Most cited references25

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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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              An updated roadmap for the integration of metal-organic frameworks with electronic devices and chemical sensors.

              Metal-organic frameworks (MOFs) are typically highlighted for their potential application in gas storage, separations and catalysis. In contrast, the unique prospects these porous and crystalline materials offer for application in electronic devices, although actively developed, are often underexposed. This review highlights the research aimed at the implementation of MOFs as an integral part of solid-state microelectronics. Manufacturing these devices will critically depend on the compatibility of MOFs with existing fabrication protocols and predominant standards. Therefore, it is important to focus in parallel on a fundamental understanding of the distinguishing properties of MOFs and eliminating fabrication-related obstacles for integration. The latter implies a shift from the microcrystalline powder synthesis in chemistry labs, towards film deposition and processing in a cleanroom environment. Both the fundamental and applied aspects of this two-pronged approach are discussed. Critical directions for future research are proposed in an updated high-level roadmap to stimulate the next steps towards MOF-based microelectronics within the community.
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                Author and article information

                Journal
                ACS Cent Sci
                ACS Cent Sci
                oc
                acscii
                ACS Central Science
                American Chemical Society
                2374-7943
                2374-7951
                10 December 2019
                26 December 2019
                : 5
                : 12
                : 1959-1964
                Affiliations
                []Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02138, United States
                [22] Department of Physics and John A. Paulson School of Engineering and Applied Sciences, Harvard University , Cambridge, Massachusetts 02138, United States
                [§ ]Department of Chemistry, University of California Berkeley , Berkeley, California 94720, United States
                []Department of Chemistry, Materials Science & Engineering, Biomedical Engineering, International Institute for Nanotechnology, Northwestern University , Evanston, Illinois 60208, United States
                []Innovation Partnership Building, University of Connecticut , Storrs, Connecticut 06269, United States
                [# ]Department of Chemistry and Biochemistry, University of Oregon , Eugene, Oregon 97401, United States
                Author notes
                Article
                10.1021/acscentsci.9b01006
                6936098
                31893225
                c76a4aad-c2f7-4e4b-9fc9-208680bf2a7f
                Copyright © 2019 American Chemical Society

                This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.

                History
                : 02 October 2019
                Categories
                Research Article
                Custom metadata
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                oc9b01006

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