Sequence-defined oligo( ortho -arylene) foldamers derived from the benzannulation of ortho (arylene ethynylene)s
Abstract
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.
- Authors:
-
[1];
[1]
- Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, USA
- Department of Physics, University of California at Berkeley, Berkeley, USA
- Nuclear Magnetic Resonance Laboratory, Cornell University, Ithaca, USA
- X-ray Crystallography Laboratory, Cornell University, Ithaca, USA
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1490500
- Alternate Identifier(s):
- OSTI ID: 1624940
- Grant/Contract Number:
- AC02-05CH11231; W911NF-15-1-0447; NSF [CHE-1124754]; NSF GRFP [DGE-1144153]; NSF MRSEC program [DMR-1120296]; NSF-MRI program [CHE-1531632]; NIH [1S10OD012254-01A1]
- Resource Type:
- Published Article
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Name: Chemical Science Journal Volume: 7 Journal Issue: 10; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry (RSC)
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry
Citation Formats
Lehnherr, Dan, Chen, Chen, Pedramrazi, Zahra, DeBlase, Catherine R., Alzola, Joaquin M., Keresztes, Ivan, Lobkovsky, Emil B., Crommie, Michael F., and Dichtel, William R. Sequence-defined oligo( ortho -arylene) foldamers derived from the benzannulation of ortho (arylene ethynylene)s. United Kingdom: N. p., 2016.
Web. doi:10.1039/C6SC02520J.
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. United Kingdom. https://doi.org/10.1039/C6SC02520J
Lehnherr, Dan, Chen, Chen, Pedramrazi, Zahra, DeBlase, Catherine R., Alzola, Joaquin M., Keresztes, Ivan, Lobkovsky, Emil B., Crommie, Michael F., and Dichtel, William R. Mon .
"Sequence-defined oligo( ortho -arylene) foldamers derived from the benzannulation of ortho (arylene ethynylene)s". United Kingdom. https://doi.org/10.1039/C6SC02520J.
@article{osti_1490500,
title = {Sequence-defined oligo( ortho -arylene) foldamers derived from the benzannulation of ortho (arylene ethynylene)s},
author = {Lehnherr, Dan and Chen, Chen and Pedramrazi, Zahra and DeBlase, Catherine R. and Alzola, Joaquin M. and Keresztes, Ivan and Lobkovsky, Emil B. and Crommie, Michael F. and Dichtel, William R.},
abstractNote = {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.},
doi = {10.1039/C6SC02520J},
journal = {Chemical Science},
number = 10,
volume = 7,
place = {United Kingdom},
year = {Mon Sep 19 00:00:00 EDT 2016},
month = {Mon Sep 19 00:00:00 EDT 2016}
}
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https://doi.org/10.1039/C6SC02520J
https://doi.org/10.1039/C6SC02520J
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Cited by: 32 works
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Figures / Tables:
Scheme 1: Synthetic approaches to o-arylenes.
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