title: Palladium-Mediated Surface-Initiated Kumada Catalyst Polycondensation: A Facile Route Towards Oriented Conjugated Polymers.
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.
authors.affiliation: Department of Chemistry and College of Engineering, University of Georgia, Riverbend Research South, 220 Riverbend Road, Athens, Georgia 30602, USA.
authors.forename: N Eric
authors.initials: NE
authors.lastname: Huddleston
authors.affiliation: Department of Chemistry and College of Engineering, University of Georgia, Riverbend Research South, 220 Riverbend Road, Athens, Georgia 30602, USA.
authors.forename: S Kyle
authors.initials: SK
authors.lastname: Sontag
authors.affiliation: Department of Chemistry and College of Engineering, University of Georgia, Riverbend Research South, 220 Riverbend Road, Athens, Georgia 30602, USA.
authors.forename: Jenna A
authors.initials: JA
authors.lastname: Bilbrey
authors.affiliation: Department of Chemistry and College of Engineering, University of Georgia, Riverbend Research South, 220 Riverbend Road, Athens, Georgia 30602, USA.
authors.forename: Gareth R
authors.initials: GR
authors.lastname: Sheppard
authors.affiliation: Department of Chemistry and College of Engineering, University of Georgia, Riverbend Research South, 220 Riverbend Road, Athens, Georgia 30602, USA. jlocklin@uga.edu.
authors.forename: Jason
authors.initials: J
authors.lastname: Locklin
mesh_terms: D016880:Anisotropy; D001965:Bromides / Q000737:chemistry; D002384:Catalysis; D055664:Electrochemical Techniques; D005296:Ferrous Compounds / Q000737:chemistry*; D017616:Magnesium Compounds / Q000737:chemistry; D008567:Membranes, Artificial; D000075163:Metallocenes; D018625:Microscopy, Atomic Force; D010165:Palladium / Q000737:chemistry*; D011108:Polymers / Q000737:chemistry*; D013499:Surface Properties; D013876:Thiophenes / Q000737:chemistry*
chemical_list: D001965:Bromides; D005296:Ferrous Compounds; D017616:Magnesium Compounds; D008567:Membranes, Artificial; D000075163:Metallocenes; D011108:Polymers; D013876:Thiophenes; C586611:magnesium bromide; D010165:Palladium; C062788:poly(3-methylthiophene); C004998:ferrocene