Single‐Step Gas‐Phase Polyperfluoroalkylation of Naphthalene Leads to Thermodynamic Products

High-temperature gas-phase, solvent- and catalyst-free reaction of naphthalene with an excess of RFI reagent (RFCF3, C2F5, n-C3F7, and n-C4F9) was used for the first time to produce a series of highly perfluoroalkylated naphthalene products NAPH(RF)n with n=2–5. Four 95+ % pure 1,3,5,7-NAPH(RF)4 with RFCF3, C2F5, n-C3F7, and n-C4F9 were isolated using a simple chromatography-free procedure. These new compounds were fully characterized by 19F and 1H NMR spectroscopy, X-ray crystallography (for RFCF3 and C2F5), atmospheric-pressure chemical ionization mass spectrometry, and cyclic and square-wave voltammetry. DFT calculations confirm that the proposed synthesis yields the most stable isomers that have not been accessed by alternative preparation techniques.