Fluorine segregation in the solid state organisation of the 12 mixed-valence salt of bis(2,2-difluoropropylenedithio)tetrathiafulvalene with the isosteric nickel dithiolene complex

Olivier J. Dautel (1) , Marc Fourmigué (2) , Eric Faulques (1)

1 IMN - Institut des Matériaux Jean Rouxel
2 MATéRIAUX ET INTERFACES (CIMI) - FRE 2447 CNRS-Université d'Angers

Electrooxidation of the nickel dithiolene complex [Ni(F2pdt)2]–(F2pdt2–= 6,6-difluoro-6,7-dihydro-5H-[1,4]dithiepine-2,3-dithiolato) in the presence of the isosteric bis(2,2-difluoropropylenedithio)tetrathiafulvalene 1 donor molecule affords a 12 salt, formulated as [1][Ni(F2pdt)2]2, whose layered structure is isostructural with that of 1, and is characterised by a segregation of the fluorinated moieties into fluorous bilayers. It crystallises in the monoclinic system, space group P21/c with a= 15.227(3), b= 4.6395(9), c= 13.098(3)Å, = 113.96(3)°, Z= 2, R= 0.0388 for 804 reflections with I > 2(I). Structural, electronic and micro-Raman studies demonstrate the mixed-valence character of the salt.

Domaines: Chimie organique; Matériaux; Cristallographie

Olivier J. Dautel, Marc Fourmigué, Eric Faulques. Fluorine segregation in the solid state organisation of the 12 mixed-valence salt of bis(2,2-difluoropropylenedithio)tetrathiafulvalene with the isosteric nickel dithiolene complex. CrystEngComm, 2002, 4 (45), pp.249-261. ⟨10.1039/b202663e⟩. ⟨hal-00177984⟩