AMHB: (Anti)aromaticity-modulated hydrogen bonding

Tayeb Kakeshpour, Judy I. Wu, James E. Jackson

    Research output: Contribution to journalArticle

    • 4 Citations

    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.

    Original languageEnglish (US)
    Pages (from-to)3427-3432
    Number of pages6
    JournalJournal of the American Chemical Society
    Volume138
    Issue number10
    DOIs
    StatePublished - Mar 16 2016

    Profile

    Pharmaceutical Chemistry
    Dimerization
    Hydrogen Bonding
    Computer Simulation
    Molecular Biology
    Hydrogen
    Electrons
    Aldosterone
    Agaricales
    Surgical Hemostasis
    Leghemoglobin
    Echoencephalography
    Daphnia
    Molecular biology
    Chemical shift
    Self assembly
    Hydrogen bonds

    ASJC Scopus subject areas

    • Chemistry(all)
    • Catalysis
    • Biochemistry
    • Colloid and Surface Chemistry

    Cite this

    AMHB : (Anti)aromaticity-modulated hydrogen bonding. / Kakeshpour, Tayeb; Wu, Judy I.; Jackson, James E.

    In: Journal of the American Chemical Society, Vol. 138, No. 10, 16.03.2016, p. 3427-3432.

    Research output: Contribution to journalArticle

    Kakeshpour, Tayeb; Wu, Judy I.; Jackson, James E. / AMHB : (Anti)aromaticity-modulated hydrogen bonding.

    In: Journal of the American Chemical Society, Vol. 138, No. 10, 16.03.2016, p. 3427-3432.

    Research output: Contribution to journalArticle

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    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.",
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