In the present paper, the peculiar orientational behavior, studied by liquid crystal NMR (LXNMR) spectroscopy, of the D(2d) symmetry quasi-spherical molecule of tetramethylallene (TMA) dissolved in the nematic solvent I52 is exploited to attempt a quantitative experimental assessment of the correlation between molecular vibrations and overall rotations in weakly oriented molecules. The analysis of the very small D(HH) and (1)D((13)C-H) dipolar couplings, available from the natural abundance LXNMR spectra of TMA at different temperatures, allows for a derivation leading (by making a few approximations) to the quantification of the vibration-reorientation (also called nonrigid) contribution affecting the observed direct (1)D((13)C-H) dipolar coupling. The obtained results show that, under the particular conditions of the studied system (very weak orientational ordering of a highly symmetric molecule), this contribution is particularly important, in order to reproduce the whole value of the "observed" dipolar coupling. This issue is discussed and commented on at length in the work, also, by making reference to the analogy with perfectly symmetric molecules (such as methane and analogues) dissolved in liquid crystalline phases.
© 2011 American Chemical Society