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AMHB: (Anti)aromaticity-Modulated Hydrogen Bonding

Author:
Kakeshpour, Tayeb, Wu, Judy I., Jackson, James E.
Source:
Journal of the American Chemical Society 2016 v.138 no.10 pp. 3427-3432
ISSN:
1520-5126
Subject:
dimerization, hydrogen, hydrogen bonding, molecular biology, surveys
Abstract:
This in silico survey shows that changes in the (anti)aromatic character of π-conjugated heterocycles can be used to fine-tune their hydrogen (H-)bond strengths. Upon H-bonding dimerization, the π-electrons of these rings can be polarized to reinforce or disrupt their (anti)aromatic π-conjugated circuits (πCCs) and stabilize or destabilize the resulting H-bonded complexes. H-bonding interactions that enhance aromaticity or relieve antiaromaticity are fortified, whereas those that intensify antiaromaticity or disrupt aromaticity are weakened, relative to analogues lacking full π-circuits. Computed dissected nucleus-independent chemical shifts, NICS(1)zz, reveal a uniform pattern and document changes in the magnetic (anti)aromatic character of the heterocycles considered. Recognition of this (anti)aromaticity-modulated H-bonding (AMHB) phenomenon offers insights into a range of fields from organocatalysis and self-assembly to pharmaceutical chemistry and molecular biology.
Agid:
5418404