Ligand Design for Luminescent Lanthanide-Containing Metallopolymers

The isolation of emissive materials with lanthanide ions is a topic of interest for imaging, display, and sensing applications, and it requires tuning of the electronics of the systems, such that, during the process of sensitization of the metal-centered luminescence, energy transfer from the sensitizer to the lanthanide ion is efficient and the resulting materials have the characteristics required for a given application. We discuss here our group's work in controlling the singlet-and triplet-state energies of sensitizing ligands through the choice of functional groups on the pyridine rings chelating to the lanthanide ions and show how we achieved progressively higher emission efficiencies. We describe targeted functionalization that led to highly emissive systems in solution and in the solid state and to new metallopolymers with norbornene or dicydopentadiene-based backbones and pyridinebis(oxazoline) pendants, which display red Eu-III-based, green Tb-III-based, and, for the first time, blue Tm-III-based emission.