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      Topochemical conversion of a dense metal–organic framework from a crystalline insulator to an amorphous semiconductor†

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          Abstract

          A dense, insulating metal–organic framework (MOF), is successfully converted into a semiconducting amorphous MOF via a topochemical route.

          Abstract

          The topochemical conversion of a dense, insulating metal–organic framework (MOF) into a semiconducting amorphous MOF is described. Treatment of single crystals of copper( i) chloride trithiocyanurate, Cu ICl(ttcH 3) (ttcH 3 = trithiocyanuric acid), 1, in aqueous ammonia solution yields monoliths of amorphous Cu I 1.8(ttc) 0.6(ttcH 3) 0.4, 3. The treatment changes the transparent orange crystals of 1 into shiny black monoliths of 3 with retention of morphology, and moreover increases the electrical conductivity from insulating to semiconducting (conductivity of 3 ranges from 4.2 × 10 –11 S cm –1 at 20 °C to 7.6 × 10 –9 S cm –1 at 140 °C; activation energy = 0.59 eV; optical band gap = 0.6 eV). The structure and properties of the amorphous conductor are fully characterized by AC impedance spectroscopy, X-ray photoelectron spectroscopy, X-ray pair distribution function analysis, infrared spectroscopy, diffuse reflectance spectroscopy, electron spin resonance spectroscopy, elemental analysis, thermogravimetric analysis, and theoretical calculations.

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          Most cited references 48

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          Functional Porous Coordination Polymers

          The chemistry of the coordination polymers has in recent years advanced extensively, affording various architectures, which are constructed from a variety of molecular building blocks with different interactions between them. The next challenge is the chemical and physical functionalization of these architectures, through the porous properties of the frameworks. This review concentrates on three aspects of coordination polymers: 1). the use of crystal engineering to construct porous frameworks from connectors and linkers ("nanospace engineering"), 2). characterizing and cataloging the porous properties by functions for storage, exchange, separation, etc., and 3). the next generation of porous functions based on dynamic crystal transformations caused by guest molecules or physical stimuli. Our aim is to present the state of the art chemistry and physics of and in the micropores of porous coordination polymers.
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            Two-dimensional detector software: From real detector to idealised image or two-theta scan

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              Luminescent metal-organic frameworks.

              Metal-organic frameworks (MOFs) display a wide range of luminescent behaviors resulting from the multifaceted nature of their structure. In this critical review we discuss the origins of MOF luminosity, which include the linker, the coordinated metal ions, antenna effects, excimer and exciplex formation, and guest molecules. The literature describing these effects is comprehensively surveyed, including a categorization of each report according to the type of luminescence observed. Finally, we discuss potential applications of luminescent MOFs. This review will be of interest to researchers and synthetic chemists attempting to design luminescent MOFs, and those engaged in the extension of MOFs to applications such as chemical, biological, and radiation detection, medical imaging, and electro-optical devices (141 references).
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                Author and article information

                Journal
                Chem Sci
                Chem Sci
                Chemical Science
                Royal Society of Chemistry
                2041-6520
                2041-6539
                1 February 2015
                1 December 2014
                : 6
                : 2
                : 1465-1473
                Affiliations
                [a ] Department of Materials Science and Metallurgy , University of Cambridge , Charles Babbage Road , Cambridge CB3 0FS , UK . Email: akc30@ 123456cam.ac.uk ; Fax: +44 (0) 1223 334567 ; Tel: +44 (0) 1223 767061
                [b ] International Center for Materials Nanoarchitectonics (WPI-MANA) , National Institute for Materials Science (NIMS) , 1-1 Namiki , Ibaraki 305-0044 , Japan . Email: TOMINAKA.Satoshi@ 123456nims.go.jp ; Tel: +81 29 860 4594
                [c ] Waseda Institute for Advanced Study (WIAS) , Waseda University , 3-4-1 Okubo, Shinjuku , Tokyo 169-8555 , Japan
                [d ] Department of Chemistry , University of Oxford , Inorganic Chemistry Laboratory , South Parks Road , Oxford, OX1 3QR , UK
                Article
                c4sc03295k
                10.1039/c4sc03295k
                5811114
                This journal is © The Royal Society of Chemistry 2014

                This is an Open Access article distributed under the terms of the Creative Commons Attribution 3.0 Unported License ( http://creativecommons.org/licenses/by/3.0/) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

                Categories
                Chemistry

                Notes

                †Electronic supplementary information (ESI) available: PXRD, impedance, TGA, IR, XPS, PDF, ESR, and CIF files. CCDC 1018776–1018778. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc03295k

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