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Enantiotopic discrimination in the NMR spectra of prochiral rigid solutes in chiral liquid crystals (CLC), by the ordering mechanism, is limited to molecules possessing one of the four, so called, "allowed" symmetries, D2d, C2v, Cs, and S4. So far, such spectral discrimination was demonstrated only for solutes possessing one of the first three symmetries. In this work, we present deuterium NMR measurements on a rigid S4 compound dissolved in a chiral nematic solvent and demonstrate, for the first time, enantiotopic discrimination in such symmetry. The measurements were performed on the isotopically normal icosane derivative (1) and on its isotopomer (1−d8), specifically deuterated in its four core methylene groups. As a CLC solvent, a lyotropic mesophase, consisting of a solution of poly−γ−benzyl−L−glutamate (PBLG) in pyridine, was employed. For comparison with a corresponding achiral liquid crystal (ALC) solvent, a solution of a racemic mixture of poly−γ−benzylglutamate (PBG) of similar composition in the same co−solvent was used. The spectra were recorded at 92.1 MHz using the 2D Q−COSY Fz sequence with proton decoupling. In the CLC solvents they exhibited clear discrimination due to different enantiotopic sites, with components displaced symmetrically, at frequencies below and above those in the corresponding ALC, as expected for discrimination by ordering. Two procedures were employed for correlating the enantiotopic sites in the CLC spectra. For 1−d8 the dipolar cross−peaks in a 2D 2H−2H COSY−90 experiment provided identification of signals belonging to the same methylene (and hence the same enantiotopic) groups. For 1 the correlation was achieved using a least−square−deviation fitting of the experimental quadrupole splittings with respect to those expected from the molecular geometry. These results, with appropriate symmetry considerations were used to determine the symmetric (Szz) and antisymmetric (Sxy and Sxx−Syy) components of the Saupe ordering matrix. Interpretation of the NMR spectra of prochiral solutes in CLC suffers from the ambiguity in identifying the signals with specific enantiotopic groups. For this reason only the relative (but not the absolute) signs of the antisymmetric elements of the ordering matrix can be determined. For the S4 group this leads to sign ambiguity in the rhombic term in the diagonalized ordering matrix. Similar (but not identical) ambiguities occur for solutes belonging to the other allowed groups. In a concluding section of the paper, the ambiguities in the antisymmetric order parameters for the various allowed groups are compared and their physical meaning are discussed
