Journal
MACROMOLECULAR RAPID COMMUNICATIONS
Volume 33, Issue 24, Pages 2115-2120Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/marc.201200472
Keywords
conjugated polymers; palladium cross-coupling; SI-KCTP
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Funding
- National Science Foundation [CHE 1058631, DMR 0953112]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1058631] Funding Source: National Science Foundation
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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 x 1014 molecules per cm2). UVVis 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 UVVis spectroscopy, which indicates a degree of orientation perpendicular to the substrate. Evidence that palladium can maintain p-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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