Lanthanide luminescence in Pybox functionalized metallopolymers
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Lanthanide luminescence is woven into the fabric of modern day existence. Due to their narrow emission and useful red and green emission Eu(III) and Tb(III) have been extensively studied and applied as phosphors in a number of devices. It is in the pursuit of ever improving these devices' emission efficiency, as well as increasing the number of light emitting materials, that we continue to develop novel sensitizing antennas. It was shown that the incorporation of Pybox-derivatives into polymers results in luminescent solids with high quantum efficiencies. Two Pybox monomers were synthesized and studied in detail. These monomers were copolymerized with three co-monomers through either radical polymerization in one case or through ring opening metathesis polymerization in the other case. Derivatizing the pyridine ring of Ph2Pybox with a vinylbenzyl group lead to a monomer capable of sensitizing Eu(III) but not Tb(III) emission due to its triplet state energy. Grafting the Ph2Pybox derivative onto poly(vinylbenzyl chloride) and subsequent treatment with Eu(III) nitrate gave red light emitting solids with high quantum yields. Emission efficiencies were dependent on metal coordination site densities on the polymer backbone. A Pybox-derivative with a norbornene para-functional group sensitized the emission of Eu(III) and Tb(III) in near equal efficiencies. This monomer was copolymerized with DCPD and norbornene, also showing that the quantum yields were influenced by coordination site ratios to polymer repeat unit. Mixed Ln(III) metal species were prepared with Eu(III), Tb(III) and Tm(III) resulting in mixed color emission, creating the potential for solid single phase white light emitters.