Topochemical conversion of a dense metal-organic framework from a crystalline insulator to an amorphous semiconductor
Tominaka, S Hamoudi, H Suga, T Bennett, T.D Cairns, A.B Cheetham, A.K
Tominaka, S
Hamoudi, H
Suga, T
Bennett, T.D
Cairns, A.B
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Alternative Title
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. © The Royal Society of Chemistry 2015.
Keywords
Activation energy, Amorphous semiconductors, Chemicals removal (water treatment), Chlorine compounds, Crystalline materials, Distribution functions, Electron spin resonance spectroscopy, Energy gap, Infrared spectroscopy, Java programming language, Magnetic moments, Metal analysis, Organometallics, Single crystals, Spectroscopy, Spectrum analysis, Thermogravimetric analysis, Ac impedance spectroscopy, Aqueous ammonia solution, Diffuse reflectance spectroscopy, Electrical conductivity, Metal organic framework, Pair distribution function analysis, Structure and properties, Theoretical calculations, X ray photoelectron spectroscopy
Source Title
Chemical Science
Publisher
Royal Society of Chemistry
Series/Report No.
Collections
Rights
Attribution 4.0 International
Date
2015
DOI
10.1039/c4sc03295k
Type
Article