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New charge transfer salts of two organic π-donors of the tetrathiafulvalene type with the paramagnetic [Cr(NCS)6]3- anion

Abstract : The electrochemical combination of the paramagnetic anion [Cr(NCS)6]3- with the organic π-donors bis(ethylenedithio)tetrathiafulvalene (ET) and 4,5-bis(2-hydroxyethylthio) -4′,5′-ethylenedithiotetrathiafulvalene (DHET-EDTTTF) leads to two new radical cation salts, namely (ET)4 [Cr(NCS 6]·PhCN 1 and (DHET-EDTTTF)2 (NEt4)[Cr(NCS)6] 2. Both have been characterized by X-ray crystallography, magnetic and resistivity measurements. The structure of 1 consists of alternating inorganic layers generated by the anions and organic layers in which the PhCN molecules are inserted; the organic sub-lattice is built up from four different ET units, three of them with a charge distribution of +1, the fourth being neutral. The organic sub-lattice of 2 contains a centrosymmetric [(DHET-EDTTTF•)2]2+ dimer, in which the overlap mode is of the eclipsed type. Conductivity measurements indicate that compounds 1 and 2 are semiconductors with room temperature conductivities of 1.4 × 10-2 and 6.1 × 10-5 S cm-1 and activation energies of 0.24 and 0.23 eV, in 1 and 2, respectively. For both salts, magnetic measurements indicate (i) that the organic and inorganic parts are magnetically independent, and (ii) that the organic units are antiferromagnetically coupled. To cite this article: F. Thétiot et al., C. R. Chimie 6 (2003). © 2003 Académie des sciences. Published by Éditions scientifiques et médicales Elservier SAS. All rights reserved.
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Submitted on : Wednesday, April 11, 2018 - 2:59:00 PM
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Franck Thétiot, F. Bérézovsky, Smail Triki, J.S. Pala, C.J. Gómez-García, et al.. New charge transfer salts of two organic π-donors of the tetrathiafulvalene type with the paramagnetic [Cr(NCS)6]3- anion. Comptes Rendus Chimie, Elsevier Masson, 2003, 6 (3), pp.291-300. ⟨10.1016/S1631-0748(03)00046-8⟩. ⟨hal-01763889⟩

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