A general strategy for obtaining 19F-19F and 13C-19F residual dipolar couplings in perfluorocarbons from the NMR spectroscopy of liquid crystalline samples.
A two-dimensional Fluorine Detected Local Field (FDLF) NMR experiment is demonstrated on a sample of perfluoropropyl iodide dissolved in the nematic solvent ZLI1132. In analogy to the proton detected local field (PDLF) technique, for each resolved site of the carbon spectrum, a simple map of the heteronuclear coupling network is obtained in the indirect dimension. A full analysis of the FDLF spectrum was achieved with the aid of two-dimensional (19)F-(13)C HETCOR and (13)C, D-resolved spectra (with D representing the anisotropic spin-spin coupling). A one-dimensional (19)F spectrum was recorded on the same sample at intermediate resolution, and values of the residual spin-spin couplings T(CF) and T(FF) obtained from both experiments were combined and used to provide starting parameters for the analysis of a very high resolution (19)F spectrum, including the weak satellite lines from single-(13)C isotopomers. The high-precision, residual, anisotropic couplings were used to explore whether they have an appreciable contribution from the anisotropic electron-mediated spin-spin couplings.
Dipartimento di Chimica, Universita della Calabria, 87030 Arcavacata di Rende, Italy.
Giuseppina
G
De Luca
James W
JW
Emsley
Elodie
E
Salager
Anne
A
Lesage