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Article Dans Une Revue European Journal of Inorganic Chemistry Année : 2014

Synthesis and Properties of a Mixed-​Valence Compound with Single-​Step Tunneling and Multiple-​Step Hopping Behavior

Résumé

The org. precursor bis(trimethylsilylethynyl)​TTFMe2 (3, TTF = tetrathiafulvalene) was prepd. as a 1:1 mixt. of the cis and trans isomers. Pure samples of 3-​cis and 3-​trans were obtained by crystn. and identified by XRD anal. The treatment of pure 3-​trans and a 1:1 mixt. of 3-​cis​/trans with (i) potassium carbonate, (ii) the iron complex Cp*(dppe)​FeCl [5, Cp* = η5-​C5Me5, dppe = 1,​2-​bis(diphenylphosphanyl)​ethane] in the presence of KPF6, and (iii) tBuOK provided Cp*(dppe)​Fe-​C C-​TTFMe2-​C C-​Fe(dppe)​Cp* as the pure geometric isomer 6-​trans (85 %) and as the 60:40 mixt. 6-​cis​/trans (63 %)​, resp. The oxidn. of 6-​trans with [(C5H5)​2Fe]​PF6 gave [6-​trans]​[PF6]​n (n = 1-​3)​. Visible, IR, near-​IR (NIR)​, and ESR (EPR) spectroscopy together with DFT data show that [6-​trans]​[PF6] is a class II mixed-​valence complex (Hab = 85 cm-​1) in which the spin distribution depends on the conformation of the mol. Intramol. electron transfer occurs through single-​step tunneling and a multistep hoping mechanism. The triplet state is thermally accessible for [6-​trans]​[PF6]​2.

Dates et versions

hal-01016872 , version 1 (01-07-2014)

Identifiants

Citer

Rim Makhoul, Yuki Kumamoto, Akira Miyazaki, Frederic Justaud, Frederic Gendron, et al.. Synthesis and Properties of a Mixed-​Valence Compound with Single-​Step Tunneling and Multiple-​Step Hopping Behavior. European Journal of Inorganic Chemistry, 2014, 2014 (24), pp.3899-3911. ⟨10.1002/ejic.201402022⟩. ⟨hal-01016872⟩
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