Bis-Tridendate Ir(III) Polymer-Metallocomplexes: Hybrid, Main-Chain Polymer Phosphors for Orange–Red Light Emission

In this work, hybrid polymeric bis-tridentate iridium(III) complexes bearing derivatives of terpyridine (tpy) and 2,6-di(phenyl) pyridine as ligands were successfully synthesized and evaluated as red-light emitters. At first, the synthesis of small molecular bis-tridendate Ir(III) complexes bearing alkoxy-, methyl-, or hydroxy-functionalized terpyridines and a dihydroxyphenyl-pyridine moiety was accomplished. Molecular complexes bearing two polymerizable end-hydroxyl groups and methyl- or alkoxy-decorated terpyridines were copolymerized with difluorodiphenyl-sulphone under high temperature polyetherification conditions. Alternatively, the post-polymerization complexation of the terpyridine-iridium(III) monocomplexes onto the biphenyl-pyridine main chain homopolymer was explored. Both cases afforded solution-processable metallocomplex-polymers possessing the advantages of phosphorescent emitters in addition to high molecular weights and excellent film-forming ability via solution casting. The structural, optical, and electrochemical properties of the monomeric and polymeric heteroleptic iridium complexes were thoroughly investigated. The polymeric metallocomplexes were found to emit in the orange–red region (550–600 nm) with appropriate HOMO and LUMO levels to be used in conjunction with blue-emitting hosts. By varying the metal loading on the polymeric backbone, the emitter’s specific emission maxima could be successfully tuned.