Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 131, Issue 45, Pages 16445-16453Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja904885w
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Funding
- Leibniz-Institut for Polymerforschung Dresden e.V.
- Deutsche Forschungsgemeinschaft [KI-1094/3-1]
- Danish Strategic Research Council [DSF 2104-05-0052, 2104-07-0022]
- EUDP [64009-0050]
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Herein, we present a new paradigm in the engineering of nanostructured hybrids between conjugated polymer and inorganic materials via a chain-growth surface-initiated Kumada catalyst-transfer, polycondensation (SI-KCTP) from particles. Poly(3-hexylthiophene), P3HT, a benchmark material for organic electronics, was selectively grown by SI-KCTP from (nano)particles bearing surface-immobilized Ni catalysts supported by bidentate phosphorus ligands, that resulted in hairy (nano)particles with end-tethered P3HT chains. Densely grafted P3HT chains exhibit strongly altered optical properties compared to the untethered counterparts (red shift and vibronic fine structure in absorption and fluorescence spectra), as a result of efficient planarization and chain-aggregation. These effects are observed in solvents that are normally recognized as good solvents for P3HT (e.g., tetrahydrofurane). We attribute this to strong interchain interactions within densely grafted P3HT chains, which can be tuned by changing the surface curvature (or size) of the supporting particle. The hairy P3HT nanoparticles were successfully applied in bulk heterojunction solar cells.
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