PtI2(5,5'-bis(HCF2CH2OCH2)-2,2'-bpy)], 55-2FH-PtI2, is the first example of a substituted fluorinated diiodoplatinum diimine complex that exhibits polymorphism. The complex, upon recrystallization, forms two different polymorphs, denoted as alpha and beta forms. The luminescence of the alpha and beta forms are the same in glassy solution at 77 K; however, in the solid state, they differ significantly. The major difference between them lies in the solid-state packing of the crystalline structure. The alpha form is a square planar polyfluorinated PtI2-containing complex. Its extended herringbone structure consists of two neighboring stacked bipyridyl planes that do not overlap. The a form emits stronger than its parent molecule, [PtI(2)bpy], and much stronger than the beta polymorph. The beta form has a slight tetrahedral distortion about the metal center that ultimately changes the geometry of the complex and decreases the d-orbital splitting from square planar. Furthermore, overlapping bipyridine rings in the extended structure of the beta form quench the emission thus resulting in a lower energy emission. Additionally, the beta form shows only one type of C-H center dot center dot center dot O intermolecular stacking interaction that can cause the moderate distortion of the metal core.