Direct heteroarylation polymerization: guidelines for defect-free conjugated polymers
| Autor: | Yuning Li, J. Terence Blaskovits, Frédéric-Georges Fontaine, Jesse Quinn, Étienne Rochette, Agnieszka Pron, Thomas Bura, Serge Beaupré, Mario Leclerc, Marc-André Légaré |
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| Rok vydání: | 2017 |
| Předmět: |
inorganic chemicals
chemistry.chemical_classification Rational design macromolecular substances 02 engineering and technology General Chemistry Polymer Conjugated system 010402 general chemistry 021001 nanoscience & nanotechnology environment and public health 01 natural sciences Combinatorial chemistry 0104 chemical sciences Chemistry chemistry.chemical_compound Monomer chemistry Polymerization health occupations Thiophene Organic chemistry 0210 nano-technology Selectivity Phosphine |
| Zdroj: | Chemical Science |
| ISSN: | 2041-6539 2041-6520 |
| Popis: | New phosphine-based ligands and DFT calculations for defect-free conjugated polymers by direct (hetero)arylation polymerization (DHAP). Direct (hetero)arylation polymerization (DHAP) has emerged as a valuable and atom-economical alternative to traditional cross-coupling methods for the synthesis of low-cost and efficient conjugated polymers for organic electronics. However, when applied to the synthesis of certain (hetero)arene-based materials, a lack of C–H bond selectivity has been observed. To prevent such undesirable side-reactions, we report the design and synthesis of new, bulky, phosphine-based ligands that significantly enhance selectivity of the DHAP process for both halogenated and non-halogenated electron-rich and electron-deficient thiophene-based comonomers. To better understand the selectivity issues, density functional theory (DFT) calculations have been performed on various halogenated and non-halogenated electron-rich and electron-deficient thiophene-based comonomers. Calculations showed that the presence of bromine atoms decreases the energy of activation (E a) of the adjacent C–H bonds, allowing undesirable β-defects for some brominated aromatic units. Both calculations and the new ligands should lead to the rational design of monomers and methods for the preparation of defect-free conjugated polymers from DHAP. |
| Databáze: | OpenAIRE |
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