Abstract The fluorine-containing metal naphthalocyanines [F 16 NcGaCl](7) and [(F 16 NcGa) 2 O](8), which represent the first examples of peripherally fluorine substituted naphthalocyanines, were synthesized, and the nonlinear optical transmission was studied. Peripheral substitution by fluorine atoms enhances the solubility and photostability of the naphthalocyanines. In particular, for the axially μ-oxo-bridged naphthalocyanine dimer 8, ...