The Pyridyl-Tag Strategy Applied to the Hydrocarbon/Perfluorocarbon Phase-Switching of a Porphyrin and a Fullerene

A new hydrocarbon/perfluorocarbon phase-switching strategy based on coordination of pyridyl-tagged molecules to a highly fluorinated dicopper-carboxylate complex possessing two accessible axial coordination sites is described. When a chloroform solution of the tetrapyridyl-substituted porphyrin 3 (0.1 mM, 2 mL) is layered on a perfluorodecalin solution of 2 (3.25 mM, 1.5 mL), complete extraction of the porphyrin into the fluorous phase is observed after 30 min of stirring. Quantitative release of both the porphyrin and 2 is achieved simply by adding excess THF to the biphasic system, the THF acting as a pyridine competing ligand. The recovered perfluorocarbon solution containing 2 can be reused for another complexation with the same efficiency. The scope of this approach is emphasized by the phase-switching of a dipyridyl-substituted fullerene, another example of a molecule for which solubilization in perfluorocarbons is very challenging.