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Palladium-Mediated Surface-Initiated Kumada Catalyst Polycondensation: A Facile Route Towards Oriented Conjugated
N Eric Huddleston1, S Kyle Sontag1, Jenna A Bilbrey1
1Department of Chemistry and College of Engineering, University of Georgia, Riverbend Research South, 220 Riverbend Road, Athens, Georgia 30602, USA.
Abstract:
Palladium-mediated surface-initiated Kumada catalyst transfer polycondensation is used to generate poly(3-methyl thiophene) films with controlled thickness up to 100 nm. The palladium initiator density is measured using cyclic voltammetry and a ferrocene-capping agent, where the surface density is found to be 55% (1.1 × 10(14) molecules per cm(2)). UV-Vis spectroscopy and AFM show increased aggregation in palladium-initiated films due to the higher grafting density of palladium initiators on the surface. The anisotropy of the P3MT films is determined using polarized UV-Vis spectroscopy, which indicates a degree of orientation perpendicular to the substrate. Evidence that palladium can maintain π-complexation even at elevated temperatures, is also shown through the exclusive intramolecular coupling of both a phenyl and thiophene-based magnesium bromide with different dihaloarenes.
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