A combination of 19F nuclear Overhauser effects (NOE) and molecular mechanics calculations are presented for delineating the spatial origin of the well-known four-bond 19F-19F COSY connections which are generally observed in the 19F NMR spectra of compounds containing perfluorinated chains. Perfluorooctanoic acid (PFOA), R(F)-palmitic acid-F13 and diethyl perfluorosuberate were used as test cases. Spin-lattice relaxation times (T1) are included and NOESY correlations through three and four bonds occur.

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