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Issue 2, 2015
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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

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.

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

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Article information


Submitted
27 Oct 2014
Accepted
01 Dec 2014
First published
01 Dec 2014

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2015,6, 1465-1473
Article type
Edge Article
Author version available

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

S. Tominaka, H. Hamoudi, T. Suga, T. D. Bennett, A. B. Cairns and A. K. Cheetham, Chem. Sci., 2015, 6, 1465 DOI: 10.1039/C4SC03295K

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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