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

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

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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 CuI1.8(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 - 1 Feb 2015
Externally publishedYes

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ASJC Scopus subject areas

  • Chemistry(all)

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