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Sequence-defined oligo(ortho-arylene) foldamers derived from the benzannulation of ortho(arylene ethynylene)s

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-s...

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Autores principales: Lehnherr, Dan, Chen, Chen, Pedramrazi, Zahra, DeBlase, Catherine R., Alzola, Joaquin M., Keresztes, Ivan, Lobkovsky, Emil B., Crommie, Michael F., Dichtel, William R.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2016
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5450445/
https://www.ncbi.nlm.nih.gov/pubmed/28567248
http://dx.doi.org/10.1039/c6sc02520j
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author Lehnherr, Dan
Chen, Chen
Pedramrazi, Zahra
DeBlase, Catherine R.
Alzola, Joaquin M.
Keresztes, Ivan
Lobkovsky, Emil B.
Crommie, Michael F.
Dichtel, William R.
author_facet Lehnherr, Dan
Chen, Chen
Pedramrazi, Zahra
DeBlase, Catherine R.
Alzola, Joaquin M.
Keresztes, Ivan
Lobkovsky, Emil B.
Crommie, Michael F.
Dichtel, William R.
author_sort Lehnherr, Dan
collection PubMed
description 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 (1)H 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.
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spelling pubmed-54504452017-05-31 Sequence-defined oligo(ortho-arylene) foldamers derived from the benzannulation of ortho(arylene ethynylene)s Lehnherr, Dan Chen, Chen Pedramrazi, Zahra DeBlase, Catherine R. Alzola, Joaquin M. Keresztes, Ivan Lobkovsky, Emil B. Crommie, Michael F. Dichtel, William R. Chem Sci Chemistry 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 (1)H 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. Royal Society of Chemistry 2016-10-01 2016-07-08 /pmc/articles/PMC5450445/ /pubmed/28567248 http://dx.doi.org/10.1039/c6sc02520j Text en This journal is © The Royal Society of Chemistry 2016 http://creativecommons.org/licenses/by-nc/3.0/ This is an Open Access article distributed under the terms of the Creative Commons Attribution-NonCommercial 3.0 Unported License (http://creativecommons.org/licenses/by-nc/3.0/) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.
spellingShingle Chemistry
Lehnherr, Dan
Chen, Chen
Pedramrazi, Zahra
DeBlase, Catherine R.
Alzola, Joaquin M.
Keresztes, Ivan
Lobkovsky, Emil B.
Crommie, Michael F.
Dichtel, William R.
Sequence-defined oligo(ortho-arylene) foldamers derived from the benzannulation of ortho(arylene ethynylene)s
title Sequence-defined oligo(ortho-arylene) foldamers derived from the benzannulation of ortho(arylene ethynylene)s
title_full Sequence-defined oligo(ortho-arylene) foldamers derived from the benzannulation of ortho(arylene ethynylene)s
title_fullStr Sequence-defined oligo(ortho-arylene) foldamers derived from the benzannulation of ortho(arylene ethynylene)s
title_full_unstemmed Sequence-defined oligo(ortho-arylene) foldamers derived from the benzannulation of ortho(arylene ethynylene)s
title_short Sequence-defined oligo(ortho-arylene) foldamers derived from the benzannulation of ortho(arylene ethynylene)s
title_sort sequence-defined oligo(ortho-arylene) foldamers derived from the benzannulation of ortho(arylene ethynylene)s
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5450445/
https://www.ncbi.nlm.nih.gov/pubmed/28567248
http://dx.doi.org/10.1039/c6sc02520j
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