High-Field NMR Spectroscopy Reveals Aromaticity-Modulated Hydrogen Bonding in Heterocycles

Tayeb Kakeshpour, John P. Bailey, Madison R. Jenner, Darya E. Howell, Richard J. Staples, Daniel Holmes, Judy I. Wu, James E. Jackson

Research output: Contribution to journalArticle

Abstract

From DNA base pairs to drug–receptor binding, hydrogen (H-)bonding and aromaticity are common features of heterocycles. Herein, the interplay of these bonding aspects is explored. H-bond strength modulation due to enhancement or disruption of aromaticity of heterocycles is experimentally revealed by comparing homodimer H-bond energies of aromatic heterocycles with analogs that have the same H-bonding moieties but lack cyclic π-conjugation. NMR studies of dimerization in C6D6 find aromaticity-modulated H-bonding (AMHB) energy effects of approximately ±30 %, depending on whether they enhance or weaken aromatic delocalization. The attendant ring current perturbations expected from such modulation are confirmed by chemical shift changes in both observed ring C−H and calculated nucleus-independent sites. In silico modeling confirms that AMHB effects outweigh those of hybridization or dipole–dipole interaction.

Original languageEnglish (US)
Pages (from-to)9842-9846
Number of pages5
JournalAngewandte Chemie - International Edition
Volume56
Issue number33
DOIs
StatePublished - Aug 7 2017

Profile

Aldosterone
Modulation
Hydrogen
Leghemoglobin
Daphnia
Dapsone
Dimerization
Nuclear magnetic resonance spectroscopy
Chemical shift
Hydrogen bonds
DNA
Nuclear magnetic resonance

Keywords

  • aromaticity
  • dimerization
  • hydrogen bonding
  • molecular recognition
  • NMR spectroscopy

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Kakeshpour, T., Bailey, J. P., Jenner, M. R., Howell, D. E., Staples, R. J., Holmes, D., ... Jackson, J. E. (2017). High-Field NMR Spectroscopy Reveals Aromaticity-Modulated Hydrogen Bonding in Heterocycles. Angewandte Chemie - International Edition, 56(33), 9842-9846. DOI: 10.1002/anie.201705023

High-Field NMR Spectroscopy Reveals Aromaticity-Modulated Hydrogen Bonding in Heterocycles. / Kakeshpour, Tayeb; Bailey, John P.; Jenner, Madison R.; Howell, Darya E.; Staples, Richard J.; Holmes, Daniel; Wu, Judy I.; Jackson, James E.

In: Angewandte Chemie - International Edition, Vol. 56, No. 33, 07.08.2017, p. 9842-9846.

Research output: Contribution to journalArticle

Kakeshpour, T, Bailey, JP, Jenner, MR, Howell, DE, Staples, RJ, Holmes, D, Wu, JI & Jackson, JE 2017, 'High-Field NMR Spectroscopy Reveals Aromaticity-Modulated Hydrogen Bonding in Heterocycles' Angewandte Chemie - International Edition, vol 56, no. 33, pp. 9842-9846. DOI: 10.1002/anie.201705023
Kakeshpour T, Bailey JP, Jenner MR, Howell DE, Staples RJ, Holmes D et al. High-Field NMR Spectroscopy Reveals Aromaticity-Modulated Hydrogen Bonding in Heterocycles. Angewandte Chemie - International Edition. 2017 Aug 7;56(33):9842-9846. Available from, DOI: 10.1002/anie.201705023

Kakeshpour, Tayeb; Bailey, John P.; Jenner, Madison R.; Howell, Darya E.; Staples, Richard J.; Holmes, Daniel; Wu, Judy I.; Jackson, James E. / High-Field NMR Spectroscopy Reveals Aromaticity-Modulated Hydrogen Bonding in Heterocycles.

In: Angewandte Chemie - International Edition, Vol. 56, No. 33, 07.08.2017, p. 9842-9846.

Research output: Contribution to journalArticle

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