At present times it is usual practice to mark biological compounds replacing an H for an F atom to study, by means of F-19 NMR spectroscopy, aspects such as binding sites and molecular folding features. This interesting methodology could nicely be improved if it is known how proximity interactions on the F atom affect its electronic structure as gauged through high-resolution F-19 NMR spectroscopy. This is the main aim of the present work and, to this end, differently substituted peri-difluoronaphthalenes are chosen as model systems. In such compounds are rationalized some interesting aspects of the diamagnetic and paramagnetic parts of the F-19 nuclear magnetic shielding tensor as well as the transmission mechanisms for the PSO and PC contributions to log indirect nuclear spin-spin coupling constants.