Sequence-defined oligo(ortho-arylene) foldamers derived from the benzannulation of ortho(arylene ethynylene)s
| Autor: | Ivan Keresztes, Michael F. Crommie, Emil B. Lobkovsky, Joaquin M. Alzola, Zahra Pedramrazi, Chen Chen, Dan Lehnherr, Catherine R. DeBlase, William R. Dichtel |
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| Rok vydání: | 2016 |
| Předmět: | |
| Zdroj: | Chemical Science. 7:6357-6364 |
| ISSN: | 2041-6539 2041-6520 |
| DOI: | 10.1039/c6sc02520j |
| Popis: | A Cu-catalyzed benzannulation reaction transforms ortho(arylene ethynylene) oligomers into ortho-arylenes. This approach circumvents iterative Suzuki cross-coupling reactions previously used to assemble hindered ortho-arylene backbones. These derivatives form helical folded structures in the solid-state and in solution, as demonstrated by X-ray crystallography and solution-state NMR analysis. DFT calculations of misfolded conformations are correlated with variable-temperature 1H and EXSY NMR to reveal that folding is cooperative and more favorable in halide-substituted naphthalenes. Helical ortho-arylene foldamers with specific aromatic sequences organize functional π-electron systems into arrangements ideal for ambipolar charge transport and show preliminary promise for the surface-mediated synthesis of structurally defined graphene nanoribbons. |
| Databáze: | OpenAIRE |
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