Functional polymers: polyoxanorbornene-based block copolymers for the separation of f-elements and luminescent conducting metallopolymers

Abstract

A new polymeric material with a polyoxanorbornene backbone and carbamoylmethylphosphine oxide, CMPO, ligand pendant groups has been synthesized, characterized, and studied. The ability of the material to selectively partition actinides utilizing a biphasic extraction strategy was tested. The polymeric materials had significantly higher (> 5-25 times) ability to extract Th4+ than the monomeric system. The molecular weight of the material affected the extraction and separation abilities. The lower molecular weight material extracted more ions, but was less discriminate for thorium(IV) over cerium(III), lanthanum(III), and europium(III), than the higher molecular weight material. Structural modifications to this system were made by creating block copolymers. The influence of additional functionalities, created by the addition of new polymeric blocks, was investigated. The ability of the material to selectively partition actinides utilizing both solid-liquid and liquid-liquid extraction strategies was tested. Extraction efficiencies comparable to liquid-liquid extractions were achieved in the solid-liquid extractions. The extraction behavior of the materials was significantly altered by the incorporation of new blocks. The incorporation of glycol chains into the system caused an increase in the uptake of thorium(IV) over the homopolymers. The incorporation of blocks of glycol chains and blocks of cross-linked hydroxcoumarian increased the selectivity significantly (XTh/Eu 2.3 – 4.5 times higher) over the homopolymer. These materials show tremendous promise as modular polymeric scaffolds.

A novel emissive tetradentate platinum complex with electropolymerizable ethylenedioxythiophene groups has been synthesized and characterized. This material has been developed for use as the active layer in polymer light-emitting diodes. Electropolymerization offers ease of processing by depositing thin films directly onto an electrode during the polymerization process. Additionally because the emitter is covalently bound in the polymer, it cannot aggregate as is the case with some small molecule emitters. The platinum complex displayed emission peaks at 510 nm and 544 nm. Electropolymerization resulted in a conductive and emissive thin film, with an emission maximum at 453 nm.