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Devic, T., Bertran, J., Domercq, B., Canadell, E., Avarvari, N., Auban-Senzier, P. & Fourmigue, M. (2001) Cation radical salts of cyano(ethylenedithio)tetrathiafulvalene with halogenated anions: annihilation of the CN center dot center dot center dot Hal interaction and stabilisation of conducting, antiferromagnetic square or chain-type salts. NEW JOURNAL OF CHEMISTRY, 25 1418–1424. 
Added by: Richard Baschera (2017-03-01 08:48:24)
Type de référence: Article
DOI: {10.1039/b104640n}
Numéro d'identification (ISBN etc.): {1144-0546}
Clé BibTeX: Devic{2001}
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Catégories: HORSIMN
Créateurs: Auban-Senzier, Avarvari, Bertran, Canadell, Devic, Domercq, Fourmigue
Consultations : 11/418
Indice de consultation : 1%
Indice de popularité : 0.25%
{The synthesis, X-ray crystal structure and electrochemical properties of 3-cyano-3',4'-ethylenedithiotetrathiafulvalene (EDT-TTF-CN, 1) are described together with electrocrystallisation experiments in the presence of various halogenated anions, I-3(-), FeBr4-, InBr4-, AuBr4-, Mo6Br142-, Mo6Cl8Br62-. X-Ray crystal structures are described for each salt, characterised by a systematic absence of any short and directional CN . . . Hal interactions, convincing evidence of the electrostatic character of this interaction, which is enhanced in the opposite situation where cationic halogenated tetrathiafulvalenes are associated with cyanide anions such as Ag(CN)(2)(-).This behaviour is further rationalised by atomic population calculations on TTF-CN and {[}TTF-CN](.+) which confirm the strong decrease of the negatively charged character of the nitrogen atom upon TTF-CN oxidation to {[}TTF-CN](.+) A conducting mixed-valence salt is obtained in {[}1](2){[}I-3],which exhibits an unusual structure with the I-3(-) anions embedded in the organic conducting layer. All the other salts contain fully oxidised {[}1](.+) radical cations, associated into diamagnetic diads in {[}1]{[}I-3], {[}1](2){[}Mo6Br14]{[}CH3CN](4) and {[}1](2){[}Mo6Cl8Br6]{[}CH3CN](4), into spin chains in the two isostructural {[}1]{[}FeBr4]and {[}1]{[}InBr4]salts and into a quadratic two-dimensional spin system in {[}1]{[}AuBr4].}
Added by: Richard Baschera  
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