“Hairy” Poly(3-hexylthiophene) Particles Prepared via Surface-Initiated Kumada Catalyst-Transfer Polycondensation

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• 作者：Volodymyr Senkovskyy ; Roman Tkachov ; Tetyana Beryozkina ; Hartmut Komber ; Ulrich Oertel ; Marta Horecha ; Vera Bocharova ; Manfred Stamm ; Suren A. Gevorgyan ; Frederik C. Krebs ; Anton Kiriy
• 刊名：Journal of the American Chemical Society
• 出版年：2009
• 出版时间：November 18, 2009
• 年：2009
• 卷：131
• 期：45
• 页码：16445-16453
• 全文大小：399K
• 年卷期：v.131,no.45(November 18, 2009)
• ISSN：1520-5126

文摘

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.