A combination of mass spectrometry, collision-induced dissociation, ion mobility mass spectrometry (IM-MS), and density functional theory (DFT) has been used to study the evolution of anionic species generated by laser-desorption of the near planar, fluorinated polycyclic aromatic hydrocarbon (PAH), C60H21F9- (s). The dominant decay process for isolated, thermally activated species C60H21F9- comprises a sequence of multiple regioselective cyclodehydrofluorination and cyclodehydrogenation reactions (eliminating HF and H-2, respectively, while forming additional pentagons and/or hexagons). The DFT calculations allow us to set narrow bounds on the structures of the resulting fragment ions by fitting structural models to experimentally determined collision cross sections. These show that the transformation of the precursor anion proceeds via a series of intermediate structures characterized by increasing curvature, ultimately leading to the closed-shell fullerene cage C-60(-) as preprogrammed by the precursor structure.