Synthesis and Characterization of Luminescent Bis-Cyclometalated PlatinumIV Complexes

Presented is the synthesis and characterization of a series of luminescent heteroleptic bis-cyclometalated platinum(IV) complexes. An oxidation-facilitated cyclometalation is employed to convert platinum(II) pendant species into bis-cyclometalated platinum(IV) dichlorides, which are transformed into the Iris-chelated diimine complexes through ligand substitution. The structure-property relationship is probed by judiciously varying substituents on both the C boolean AND N and the N boolean AND N ligands resulting in a family of complexes exhibiting blue emission, long excited-state lifetimes, and highly efficient oxygen quenching. Excited-state properties are corroborated by static and time-dependent density-functional theory calculations of both the singlet and the triplet state.