The first surface-initiated and site specific palladium-catalyzed chaingrowth Suzuki polycondensation to graft and pattern semiconducting and emissive poly[9,9-bis(2-ethylhexyl)fluorene], PF2/6, was developed. Using our method, the grafting of PF2/6 can be successfully performed from surface-immobilized brominated polystyrene films, as well as from monolayers of small-molecules initiators and (optionally) from patterned initiators. It is important that our grafting process proceeds selectively from the surface and no detectable amounts of the polymer are formed in the solution. Furthermore, the polymerization proceeds fast even at room temperature and results into grafted PF2/6 films with thicknesses up to 100 nm.

Figure 1. Mechanism of chain-growth catalyst-transfer Suzuki polycondensation and grafting of PF2/5 brush (left). AFM images (a, b) cross-section (c) and photograph of patterned PF2/6 brushes.