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The structure of the smectic B phase formed by perfluorodecylalkanes has been analyzed through the synthesis of three molecules and a careful investigation of their mesophases. Molecules with C8, C10 and a branched C11 alkyl chain were considered. The structure factor analysis of 001 reflexions is consistent with the picture of alternating electron rich and electron poor sublayers. A structural model with segregated perfluoroalkyl chains in the middle of the layer and disordered alkyl chains on each sides is proposed. This model is discussed in terms of space filling arguments: chain lengths, cross section compatibility in the layer and compactness. Infrared dichroic ratios of the CH2 and CF2 stretching modes confirm that perfluoroalkyl subunits are perpendicular to the SB layer while alkyl ones, in a quasi molten state, fill the remaining layer space.

Figure presented. Perfluoroalkyl-substituted compounds are regarded as important components of fluorophors and for the introduction of fluorous tags into organic substrates. Their syntheses in organic solvents are achieved through different methods, among which, the addition of perfluoroalkyl radicals to unsaturated bonds represents a convenient choice. On the other hand, intermolecular radical reactions in water have attracted the attention of synthetic chemists as a strategic route to carbon-carbon bond formation reactions. In this paper we undertook the intermolecular addition of perfluoroalkyl radicals on electron rich alkenes and alkenes with electron withdrawing groups in water, mediated by silyl radicals, and obtained perfluoroalkyl-substituted compounds in fairly good yields. The radical triggering events employed consist of the thermal decomposition of an azo compound and the dioxygen initiation. Our results indicate that for intermolecular carbon-carbon bond formation reactions mediated by (Me 3Si)3SiH, the decomposition of the azo compound 1,1′-azobis(cyclohexanecarbonitrile) (ACCN) is the best radical initiator. We also found that water exerts a relevant solvent effect on the rates of perfluoroalkyl radical additions onto double bonds and the H atom abstraction from the silane. Our account provides a versatile and convenient method to achieve perfluoroalkylation reactions of alkenes in water to render perfluoroalkylated alkanes as key intermediates in the synthesis of fluorophors and other fluorinated materials. This is the first report where perfluoroalkyl-substituted alkanes are synthesized through intermolecular radical carbon-carbon bond formation reactions in water, mediated by silyl radicals.