Chiral EDT-TTF precursors with one stereogenic centre: substituent size modulation of the conducting properties in the (R-EDT-TTF) 2 PF 6 (R = Me or Et) series - Aix-Marseille Université Access content directly
Journal Articles Journal of Materials Chemistry C Year : 2019

Chiral EDT-TTF precursors with one stereogenic centre: substituent size modulation of the conducting properties in the (R-EDT-TTF) 2 PF 6 (R = Me or Et) series

Nabil Mroweh
  • Function : Author
Pascale Auban-Senzier
  • Function : Author
Narcis Avarvari

Abstract

Modulation of the packing of the donors in the solid state and of the conducting behaviour is achieved in chiral radical cation salts based on the mono-alkylated donors methyl-ethylenedithio-tetrathiafulvalene (Me-EDT-TTF 1) and ethyl-ethylenedithio-tetrathiafulvalene (Et-EDT-TTF 2), underlining the paramount role of the number of stereogenic centres and substituent steric hindrance. Both donors have been prepared as racemates and then separated as pure enantiomers by chiral HPLC. Electrocrystallization experiments provided two complete series of crystalline radical cation salts formulated as [(R)-1]2PF6, [(S)-1]2PF6, and [(rac)-1]2PF6 and [(R)-2]2PF6, [(S)-2]2PF6 and [(rac)-2]PF6·(THF), respectively. The mixed valence salts of 1 show metal-like conductivity in the high temperature regime, while the radical cation salts of 2 are semiconductors, with a much higher conductivity for the enantiopure compounds than the racemic one. Tight-binding band structure calculations of the extended Hückel type performed for all the materials explain the observed conducting behaviour and show the differences in the intermolecular interactions triggered by the change of substituent between 1 and 2.
Fichier principal
Vignette du fichier
NA-2019.pdf (1.75 Mo) Télécharger le fichier
Origin : Files produced by the author(s)
Loading...

Dates and versions

hal-02469088 , version 1 (20-03-2020)

Identifiers

Cite

Nabil Mroweh, Pascale Auban-Senzier, Nicolas Vanthuyne, Enric Canadell, Narcis Avarvari. Chiral EDT-TTF precursors with one stereogenic centre: substituent size modulation of the conducting properties in the (R-EDT-TTF) 2 PF 6 (R = Me or Et) series. Journal of Materials Chemistry C, 2019, 7 (40), pp.12664-12673. ⟨10.1039/c9tc04243a⟩. ⟨hal-02469088⟩
91 View
95 Download

Altmetric

Share

Gmail Facebook Twitter LinkedIn More