Thanks to an unusual protodemethylation reaction, a series of luminescent cyclometallated platinum(II) complexes can be prepared, which incorporate a rare NC-chelating, pyridylpyridylidene ligand, in combination with OO-coordinating acetylacetonate (acac) or NO-coordinating 2-picolinate (pic) or 8-hydroxyquinolate. The acac and pic complexes show unusual dual emission in a frozen glass. A series of cyclometallated platinum(II) complexes incorporating a rare, N^C-chelating, pyridyl-pyridylidene ligand are described, in which the coordination sphere is completed by two chlorides or an L X co-ligand, namely O O-coordinating acetylacetonate (acac), or N^O-coordinating 2-picolinate (pic) or 8-hydroxyquinolinate. The acac and pic complexes have been structurally characterized in the solid state by single-crystal X-ray diffraction. These two complexes display red phosphorescence in the solid state at room temperature. In a frozen glass at 77 K, all four complexes show two broad emission bands that span much of the visible spectrum, apparently from two unequilibrated excited states.