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Magnetic Molecular Conductors Based on Bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and the Tris(chlorocyananilato)ferrate(III) Complex

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journal contribution
posted on 28.10.2019, 15:38 by Suchithra Ashoka Sahadevan, Alexandre Abhervé, Noemi Monni, Pascale Auban-Senzier, Joan Cano, Francesc Lloret, Miguel Julve, Hengbo Cui, Reizo Kato, Enric Canadell, Maria Laura Mercuri, Narcis Avarvari
Electrocrystallization of the bis­(ethylenedithio)­tetrathiafulvalene (BEDT-TTF) organic donor in the presence of the [Fe­(ClCNAn)3]3– tris­(chlorocyananilato)­ferrate­(III) paramagnetic anion in different stoichiometric ratios and solvent mixtures afforded two different hybrid systems formulated as [BEDT-TTF]4­[Fe­(ClCNAn)3]·3H2O (1) and [BEDT-TTF]5­[Fe­(ClCNAn)3]2·2CH3CN (2) (An = anilato). Compounds 1 and 2 present unusual structures without the typical segregated organic and inorganic layers, where layers of 1 are formed by Λ and Δ enantiomers of the anionic paramagnetic complex together with mixed-valence BEDT-TTF tetramers, while layers of 2 are formed by Λ and Δ enantiomers of the paramagnetic complex together with dicationic BEDT-TTF dimers and monomers. Compounds 1 and 2 show semiconducting behaviors with room-temperature conductivities of ca. 6 × 10–3 S cm–1 (ambient pressure) and 1 × 10–3 S cm–1 (under applied pressure of 12.1 GPa), respectively, due to strong dimerization between the donors. Magnetic measurements performed on compound 1 indicate weak antiferromagnetic coupling between high-spin FeIII (SFe = 5/2) and mixed-valence radical cation diyads (BEDT-TTF)2+ (Srad = 1/2) mediated by the anilate ligands, together with an important Pauli paramagnetism typical for conducting systems.