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Magnetic Molecular Conductors Based on Bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and the Tris(chlorocyananilato)ferrate(III) Complex. | LitMetric
Electrocrystallization of the bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) organic donor in the presence of the [Fe(ClCNAn)] tris(chlorocyananilato)ferrate(III) paramagnetic anion in different stoichiometric ratios and solvent mixtures afforded two different hybrid systems formulated as [BEDT-TTF][Fe(ClCNAn)]·3HO () and [BEDT-TTF][Fe(ClCNAn)]·2CHCN () (An = anilato). Compounds and present unusual structures without the typical segregated organic and inorganic layers, where layers of are formed by Λ and Δ enantiomers of the anionic paramagnetic complex together with mixed-valence BEDT-TTF tetramers, while layers of are formed by Λ and Δ enantiomers of the paramagnetic complex together with dicationic BEDT-TTF dimers and monomers. Compounds and show semiconducting behaviors with room-temperature conductivities of ca. 6 × 10 S cm (ambient pressure) and 1 × 10 S cm (under applied pressure of 12.1 GPa), respectively, due to strong dimerization between the donors. Magnetic measurements performed on compound indicate weak antiferromagnetic coupling between high-spin Fe ( = 5/2) and mixed-valence radical cation diyads (BEDT-TTF) ( = 1/2) mediated by the anilate ligands, together with an important Pauli paramagnetism typical for conducting systems.
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