title: Activation of C--H... Halogen (Cl, Br, and I) hydrogen bonds at the organic/inorganic interface in fluorinated tetrathiafulvalenes salts.
abstract: The electrocrystallization of fluorinated bis(2,2'-difluoropropylenedithio)tetrathiafulvalene (1) in the presence of linear (ICl2-, IBr2-, I2Br-) or cluster ([Mo6Cl14]2-) anions affords 1:1 and 2:1 cation radical salts such as [1][ICl2] and [1]2[Mo6Cl14].(CH3CN)2. In both salts, the 1*+ radical ion adopts a boat conformation and envelops the anion through C-H...Hal(anion) (Hal(anion) = Cl, Br, I) hydrogen bonds. This demonstrates the activating role of the neighboring electron-withdrawing CF2 moieties in the stabilization of bi- or trimolecular neutral entities. With smaller linear anions, fluorine segregation controls the solid-state associations of the bimolecular [1]*+[X] entities, and gives rise to layered materials with a limited overlap interaction between the open-shell organic cations and magnetic spin chain behavior. With the larger [Mo6Cl14]2 ions, a strong overlap interaction between radical cations gives rise to diamagnetic [1]2(2+) dimers, which alternate with the cluster anions to form hybrid organic/inorganic ...[1]2(2+)[Mo6Cl14]2... chains. This behavior is also observed in [2]2(2+)[Mo6Cl14]2-.(CH2Cl2)2, in which compound 2 is the unsymmetrically substituted (ethylenedithio)(2,2'-difluoropropylenedithio)tetrathiafulvalene. On the other hand, the unsymmetrically substituted 2,2'-difluoropropylenedithiotetrathiafulvalene (3) affords a mixed-valence 4:1 salt with [Mo6Cl14]2, which is formulated as [3]4[Mo6Cl14].(CH3CN)2. This semiconducting salt is characterized by the coexistence of both the fluorine/fluorine segregation (with solvent inclusion) and the organic/inorganic segregation (with delocalized overlap interactions). Both Csp2-H...Cl and Csp3-H...Cl hydrogen bonds facilitate the stabilization of the organic/inorganic interface and the presence of conducting organic slabs.
authors.affiliation: Sciences Moléculaires aux Interfaces, CNRS FRE 2068, Institut des Matériaux Jean Rouxel, Nantes, France.
authors.forename: O J
authors.initials: OJ
authors.lastname: Dautel
authors.forename: M
authors.initials: M
authors.lastname: Fourmigué
authors.forename: E
authors.initials: E
authors.lastname: Canadell