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

DOI: 10.1039/C4SC03295K DOI Help

Authors: S. Tominaka (University of Cambridge) , H. Hamoudi (National Institute for Materials Science, Japan) , T. Suga (Waseda University) , T. D. Bennett (University of Cambridge) , A. B. Cairns (University of Oxford) , A. K. Cheetham (University of Cambridge)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemical Science

State: Published (Approved)
Published: January 2015
Diamond Proposal Number(s): 9691

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, CuI Cl(ttcH3) (ttcH3 ¼ 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 1011 S cm1 at 20 C to 7.6 109 S cm1 at 140 C; activation energy ¼ 0.59 eV; optical band gap ¼ 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. Soli

Subject Areas: Chemistry

Instruments: I15-Extreme Conditions

Added On: 19/12/2014 20:07

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