Activation of C--H... Halogen (Cl, Br, and I) hydrogen bonds at the organic/inorganic interface in fluorinated tetrathiafulvalenes salts |
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Authors: | Dautel O J Fourmigué M Canadell E |
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Institution: | Sciences Moléculaires aux Interfaces, CNRS FRE 2068, Institut des Matériaux Jean Rouxel, Nantes, France. |
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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]2Mo6Cl14].(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]4Mo6Cl14].(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. |
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