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- Title
High-Field NMR Spectroscopy Reveals Aromaticity-Modulated Hydrogen Bonding in Heterocycles.
- Authors
Kakeshpour, Tayeb; Bailey, John P.; Jenner, Madison R.; Howell, Darya E.; Staples, Richard J.; Holmes, Daniel; Wu, Judy I.; Jackson, James E.
- 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.
- Subjects
AROMATICITY; HYDROGEN bonding; NUCLEAR magnetic resonance spectroscopy; HOMODIMERS; HETEROCYCLIC compounds
- Publication
Angewandte Chemie, 2017, Vol 129, Issue 33, p9974
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201705023