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Issue 6, 2001
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Hal⋯Hal interactions in a series of three isostructural salts of halogenated tetrathiafulvalenes. Contribution of the halogen atoms to the HOMO–HOMO overlap interactions

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Abstract

The halogenated tetrathiafulvalenes, Br2-EDT-TTF and I2-EDT-TTF were prepared by the coupling route from the corresponding 4,5-dibromo- or 4,5-diiodo-1,3-dithiole-2-thione. In the isostructural series, (Br2-EDT-TTF)2IBr2, (Br2-EDT-TTF)2I3 and (I2-EDT-TTF)2I3, noted Br2/IBr2, Br2/I3 and I2/I3 respectively, short (3.42–3.60 Å) and directional Hal⋯Hal interactions are identified between donor molecules and with the anions, stabilising rare β′ phases. These interactions play not only a structural role but also contribute to the electronic dispersion thanks to sizeable coefficients on the halogen atoms in the HOMOs of Br2-EDT-TTF and I2-EDT-TTF. The three salts behave as Mott insulators as reflected by a high room temperature conductivity (0.5 S cm−1) with an activation energy which increases in the order Br2/IBr2 (730 K), Br2/I3 (1260 K), I2/I3 (1330 K) and a weak magnetic susceptibility, which decreases abruptly below 150 K with no sign of an antiferromagnetic ground state.

Graphical abstract: Hal⋯Hal interactions in a series of three isostructural salts of halogenated tetrathiafulvalenes. Contribution of the halogen atoms to the HOMO–HOMO overlap interactions

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Publication details

The article was received on 03 Jan 2001, accepted on 20 Mar 2001 and first published on 17 Apr 2001


Article type: Paper
DOI: 10.1039/B100103P
Citation: J. Mater. Chem., 2001,11, 1570-1575
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    Hal⋯Hal interactions in a series of three isostructural salts of halogenated tetrathiafulvalenes. Contribution of the halogen atoms to the HOMO–HOMO overlap interactions

    B. Domercq, T. Devic, M. Fourmigué, P. Auban-Senzier and E. Canadell, J. Mater. Chem., 2001, 11, 1570
    DOI: 10.1039/B100103P

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