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

S. Tominaka, H. Hamoudi, Takeo Suga, T. D. Bennett, A. B. Cairns, A. K. Cheetham

    Research output: Contribution to journalArticle

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    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, CuICl(ttcH3) (ttcH3 = trithiocyanuric acid), 1, in aqueous ammonia solution yields monoliths of amorphous CuI 1.8(ttc)0.6(ttcH3)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.

    Original languageEnglish
    Pages (from-to)1465-1473
    Number of pages9
    JournalChemical Science
    Volume6
    Issue number2
    DOIs
    Publication statusPublished - 2015 Feb 1

    Fingerprint

    Amorphous semiconductors
    Metals
    Crystalline materials
    Electron spin resonance spectroscopy
    Optical band gaps
    Ammonia
    Distribution functions
    Thermogravimetric analysis
    Chlorides
    Copper
    Infrared spectroscopy
    X ray photoelectron spectroscopy
    Activation energy
    Single crystals
    X rays
    Crystals
    Chemical analysis

    ASJC Scopus subject areas

    • Chemistry(all)

    Cite this

    Topochemical conversion of a dense metal-organic framework from a crystalline insulator to an amorphous semiconductor. / Tominaka, S.; Hamoudi, H.; Suga, Takeo; Bennett, T. D.; Cairns, A. B.; Cheetham, A. K.

    In: Chemical Science, Vol. 6, No. 2, 01.02.2015, p. 1465-1473.

    Research output: Contribution to journalArticle

    Tominaka, S. ; Hamoudi, H. ; Suga, Takeo ; Bennett, T. D. ; Cairns, A. B. ; Cheetham, A. K. / Topochemical conversion of a dense metal-organic framework from a crystalline insulator to an amorphous semiconductor. In: Chemical Science. 2015 ; Vol. 6, No. 2. pp. 1465-1473.
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    AU - Suga, Takeo

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    AU - Cairns, A. B.

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