Dialkoxybithiazole: A New Building Block for Head-to-Head Polymer Semiconductors
| Autor: | Rocío Ponce Ortiz, Jordan R. Quinn, Hakan Usta, Antonio Facchetti, Jonathan W. Hennek, Zhihua Chen, Tobin J. Marks, Xugang Guo, Yu Xia, Yan Zheng |
|---|---|
| Rok vydání: | 2013 |
| Předmět: |
Electron mobility
Alkylation Polymers 02 engineering and technology 010402 general chemistry 01 natural sciences Biochemistry Catalysis Crystallinity symbols.namesake Colloid and Surface Chemistry Polymer chemistry Van der Waals radius Organic electronics chemistry.chemical_classification Molecular Structure business.industry General Chemistry Polymer 021001 nanoscience & nanotechnology 0104 chemical sciences Amorphous solid Thiazoles Semiconductor Semiconductors Solubility chemistry Chemical engineering symbols Alkoxy group Quantum Theory 0210 nano-technology business |
| Zdroj: | Journal of the American Chemical Society. 135:1986-1996 |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/ja3120532 |
| Popis: | Polymer semiconductors have received great attention for organic electronics due to the low fabrication cost offered by solution-based printing techniques. To enable the desired solubility/processability and carrier mobility, polymers are functionalized with hydrocarbon chains by strategically manipulating the alkylation patterns. Note that head-to-head (HH) linkages have traditionally been avoided because the induced backbone torsion leads to poor π-π overlap and amorphous film microstructures, and hence to low carrier mobilities. We report here the synthesis of a new building block for HH linkages, 4,4'-dialkoxy-5,5'-bithiazole (BTzOR), and its incorporation into polymers for high performance organic thin-film transistors. The small oxygen van der Waals radius and intramolecular S(thiazolyl)···O(alkoxy) attraction promote HH macromolecular architectures with extensive π-conjugation, low bandgaps (1.40-1.63 eV), and high crystallinity. In comparison to previously reported 3,3'-dialkoxy-2,2'-bithiophene (BTOR), BTzOR is a promising building block in view of thiazole geometric and electronic properties: (a) replacing (thiophene)C-H with (thiazole)N reduces steric encumbrance in -BTzOR-Ar- dyads by eliminating repulsive C-H···H-C interactions with neighboring arene units, thereby enhancing π-π overlap and film crystallinity; and (b) thiazole electron-deficiency compensates alkoxy electron-donating characteristics, thereby lowering the BTzOR polymer HOMO versus that of the BTOR analogues. Thus, the new BTzOR polymers show substantial hole mobilities (0.06-0.25 cm(2)/(V s)) in organic thin-film transistors, as well as enhanced I(on):I(off) ratios and greater ambient stability than the BTOR analogues. These geometric and electronic properties make BTzOR a promising building block for new classes of polymer semiconductors, and the synthetic route to BTzOR reported here should be adaptable to many other bithiazole-based building blocks. |
| Databáze: | OpenAIRE |
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