Structural Diversity and Physical Properties of Paramagnetic Molecular Conductors Based on Bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and the Tris(chloranilato)ferrate(III) Complex - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Inorganic Chemistry Année : 2014

Structural Diversity and Physical Properties of Paramagnetic Molecular Conductors Based on Bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and the Tris(chloranilato)ferrate(III) Complex

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1
Matteo Atzori
  • Fonction : Auteur
Flavia Pop
Pascale Auban-Senzier
  • Fonction : Auteur
Carlos Gómez-García
  • Fonction : Auteur
Enric Canadell
  • Fonction : Auteur
Flavia Artizzu
  • Fonction : Auteur
Angela Serpe
  • Fonction : Auteur
Paola Deplano
  • Fonction : Auteur
Narcis Avarvari
Maria Mercuri
  • Fonction : Auteur

Résumé

Electrocrystallization of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) in the presence of the tris(chloranilato)ferrate(III) [Fe(Cl2An)3]3– paramagnetic chiral anion in different stoichiometric ratios and solvent mixtures afforded three different hybrid systems formulated as [BEDT-TTF]3[Fe(Cl2An)3]·3CH2Cl2·H2O (1), δ-[BEDT-TTF]5[Fe(Cl2An)3]·4H2O (2), and α‴-[BEDT-TTF]18[Fe(Cl2An)3]3·3CH2Cl2·6H2O (3). Compound 1 presents an unusual structure without the typical alternating organic and inorganic layers, whereas compounds 2 and 3show a segregated organic–inorganic crystal structure where layers formed by Λ and Δ enantiomers of the paramagnetic complex, together with dicationic BEDT-TTF dimers, alternate with layers where the donor molecules are arranged in the δ (2) and α‴ (3) packing motifs. Compound 1 behaves as a semiconductor with a much lower conductivity due to the not-layered structure and strong dimerization between the fully oxidized donors, whereas 2and 3 show semiconducting behaviors with high room-temperature conductivities of ca. 2 S cm–1 and 8 S cm–1, respectively. The magnetic properties are dominated by the paramagnetic S = 5/2 [Fe(Cl2An)3]3– anions whose high-spin character is confirmed by electron paramagnetic resonance and magnetic susceptibility measurements. The correlation between crystal structure and conductivity behavior was studied by means of tight-binding band structure calculations, which support the observed conducting properties.

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Chimie
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Dates et versions

hal-03344930 , version 1 (15-09-2021)

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Matteo Atzori, Flavia Pop, Pascale Auban-Senzier, Carlos Gómez-García, Enric Canadell, et al.. Structural Diversity and Physical Properties of Paramagnetic Molecular Conductors Based on Bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and the Tris(chloranilato)ferrate(III) Complex. Inorganic Chemistry, 2014, 53 (13), Non spécifié. ⟨10.1021/ic501001r⟩. ⟨hal-03344930⟩
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