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Palladium‐Mediated Surface‐Initiated Kumada Catalyst Polycondensation: A Facile Route Towards Oriented Conjugated Polymers
Author(s) -
Huddleston N. Eric,
Sontag S. Kyle,
Bilbrey Jenna A.,
Sheppard Gareth R.,
Locklin Jason
Publication year - 2012
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.201200472
Subject(s) - palladium , polymer chemistry , condensation polymer , materials science , ferrocene , thiophene , catalysis , cyclic voltammetry , polymer , photochemistry , chemistry , organic chemistry , electrochemistry , composite material , electrode
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.