Complete series of chiral paramagnetic molecular conductors based on tetramethyl-bis(ethylenedithio)-tetrathiafulvalene (TM-BEDT-TTF) and chloranilate-bridged heterobimetallic honeycomb layers

Atzori, Matteo;Pop, Flavia;Auban Senzier, Pascale;Clérac, Rodolphe;Canadell, Enric;MERCURI, MARIA LAURA;Avarvari, Narcis

2015-01-01

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Abstract

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(Cl 2 An) 3 ] ^3- paramagnetic anion afforded a complete series of chiral magnetic molecular conductors formulated as β-[(S,S,S,S)-TM-BEDT-TTF] 3 PPh 4 [K ^IFe ^III(Cl 2 An) 3 ]·3H 2 O (1), β-[(R,R,R,R)-TM-BEDT-TTF] 3 PPh 4 [K ^IFe ^III(Cl 2 An) 3 ]·3H 2 O (2), and β-[(rac)-TM-BEDT-TTF] 3 PPh 4 [K ^IFe ^III(Cl 2 An) 3 ]·3H 2 O (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. The magnetic properties are dominated by the paramagnetic S = 5/2 [Fe(Cl 2 An) 3 ] ^3- anions whose high-spin character is confirmed by magnetic susceptibility measurements. The correlation between crystal structure and conducting behavior has been studied by means of tight-binding band structure calculations which support the observed conducting properties.