Chiral Radical Cation Salts of Me-EDT-TTF and DM-EDT-TTF with Octahedral, Linear and Tetrahedral Monoanions - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Magnetochemistry Année : 2021

Chiral Radical Cation Salts of Me-EDT-TTF and DM-EDT-TTF with Octahedral, Linear and Tetrahedral Monoanions

, , (1) , , (2) , , , (1)
1
2
Nabil Mroweh
  • Fonction : Auteur
  • PersonId : 1083461
Alexandra Bogdan
  • Fonction : Auteur
  • PersonId : 1139371
Flavia Pop
Pascale Auban-Senzier
  • Fonction : Auteur
Elsa B Lopes
  • Fonction : Auteur
  • PersonId : 1083463
Manuel Almeida
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  • PersonId : 1083464
Narcis Avarvari

Résumé

Methyl-ethylenedithio-tetrathiafulvalene (Me-EDT-TTF (1) and dimethyl-ethylenedithio-tetrathiafulvalene (DM-EDT-TTF (2) are valuable precursors for chiral molecular conductors, which are generally obtained by electrocrystallization in the presence of various counter-ions. The number of the stereogenic centers, their relative location on the molecule, the nature of the counter-ion and the electrocrystallization conditions play a paramount role in the crystal structures and conducting properties of the resulting materials. Here, we report the preparation and detailed structural characterization of the following series of radical cation salts: (i) mixed valence (1)2AsF6 as racemic, and (S) and (R) enantiomers; (ii) [(S)-1]AsF6·C4H8O and [(R)-1]AsF6·C4H8O where a strong dimerization of the donors is observed; (iii) (1)I3 and (2)I3 as racemic and enantiopure forms and (iv) [(meso)-2]PF6 and [(meso)-2]XO4 (X = Cl, Re), based on the new donor (meso)-2. In the latter, the two methyl substituents necessarily adopt axial and equatorial conformations, thus leading to a completely different packing of the donors when compared to the chiral form (S,S)/(R,R) of 2 in its radical cation salts. Single crystal resistivity measurements, complemented by thermoelectric power measurements in the case of (1)2AsF6, suggest quasi-metallic conductivity for the latter in the high temperature regime, with σRT ≈ 1–10 S cm–1, while semiconducting behavior is observed for the (meso)-2 based salts.
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hal-03452274 , version 1 (26-11-2021)

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Paternité - CC BY 4.0

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Nabil Mroweh, Alexandra Bogdan, Flavia Pop, Pascale Auban-Senzier, Nicolas Vanthuyne, et al.. Chiral Radical Cation Salts of Me-EDT-TTF and DM-EDT-TTF with Octahedral, Linear and Tetrahedral Monoanions. Magnetochemistry, 2021, 7 (6), pp.87. ⟨10.3390/magnetochemistry7060087⟩. ⟨hal-03452274⟩
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