Complete Series of Chiral Paramagnetic Molecular Conductors Based on Tetramethyl-bis(ethylenedithio)-tetrathiafulvalene (TM-BEDT-TTF) and Chloranilate-Bridged Heterobimetallic Honeycomb Layers - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Inorganic Chemistry Année : 2015

Complete Series of Chiral Paramagnetic Molecular Conductors Based on Tetramethyl-bis(ethylenedithio)-tetrathiafulvalene (TM-BEDT-TTF) and Chloranilate-Bridged Heterobimetallic Honeycomb Layers

Résumé

Electrocrystallization of enantiopure (S,S,S,S)- and (R,R,R,R)-tetramethyl-bis(ethylenedithio)-tetrathiafulvalene (TM-BEDT-TTF) donors, as well as the racemic mixture, in the presence of potassium cations and the tris(chloranilato)- ferrate(III) [Fe(Cl2An)3]3− paramagnetic anion afforded a complete series of chiral magnetic molecular conductors f o r m u l a t e d a s β - [ ( S , S , S , S ) - T M - B E D T - TTF]3PPh4[KIFeIII(Cl2An)3]·3H2O (1), β-[(R,R,R,R)-TMBEDT- TTF]3PPh4[KIFeIII(Cl2An)3]·3H2O (2), and β-[(rac)- TM-BEDT-TTF]3PPh4[KIFeIII(Cl2An)3]·3H2O (3). Compounds 1−3 are isostructural and crystallize in triclinic space groups (P1 for 1 and 2, P−1 for 3) showing a segregated organic−inorganic crystal structure, where anionic honeycomb layers obtained by self-assembling of the Λ and Δ enantiomers of the paramagnetic complex with potassium cations alternate with organic layers where the chiral donors are arranged in the β packing motif. Compounds 1−3 show a molecular packing strongly influenced by the topology of the inorganic layers and behave as molecular semiconductors with room-temperature conductivity values of ca. 3 × 10−4 S cm−1.....

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Matériaux
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Dates et versions

hal-01140034 , version 1 (07-04-2015)

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Matteo Atzori, Flavia Pop, Pascale Auban-Senzier, Rodolphe Clérac, Enric Canadell, et al.. Complete Series of Chiral Paramagnetic Molecular Conductors Based on Tetramethyl-bis(ethylenedithio)-tetrathiafulvalene (TM-BEDT-TTF) and Chloranilate-Bridged Heterobimetallic Honeycomb Layers. Inorganic Chemistry, 2015, 54, pp. 3643-3653. ⟨10.1021/acs.inorgchem.5b00261⟩. ⟨hal-01140034⟩
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