AMHB: (Anti)aromaticity-Modulated Hydrogen Bonding

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

doi:10.1021/jacs.5b12703

Cited by 29 publications

(32 citation statements)

References 66 publications

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“…104 They reported that hydrogen bonds are stronger than expected when they increase [4n + 2] cyclic π-electron delocalization (aromaticity gain) in the hydrogen bonding compounds, and are weaker than expected when they decrease [4n + 2] cyclic π-electron delocalization (aromaticity loss) in compounds (Figure 13a). Later works from Wu and Jackson et al 105,106 extended the original idea to show that the opposite happens for [4n] "antiaromatic" rings, and these reciprocal relationships were later applied to rationalize the trends of hydrogen bonding in self-assembling systems, 80,[107][108][109] in multipoint arrays, 78,79 and may rationalize short, strong hydrogen bonds in enzymes. 110 Whether light irradiation strengthens or weakens a hydrogen bond also can be related to changes in (anti)aromaticity of hydrogen bonding compounds in the excited state.…”

Section: Aromaticity and Antiaromaticitymentioning

confidence: 99%

Hydrogen bond design principles

Karas

Das

et al. 2020

WIREs Comput Mol Sci

103

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Hydrogen bonding principles are at the core of supramolecular design. This overview features a discussion relating molecular structure to hydrogen bond strengths, highlighting the following electronic effects on hydrogen bonding: electronegativity, steric effects, electrostatic effects, π-conjugation, and network cooperativity. Historical developments, along with experimental and computational efforts, leading up to the birth of the hydrogen bond concept, the discovery of nonclassical hydrogen bonds (C H…O, O H…π, dihydrogen bonding), and the proposal of hydrogen bond design principles (e.g., secondary electrostatic interactions, resonance-assisted hydrogen bonding, and aromaticity effects) are outlined. Applications of hydrogen bond design principles are presented.

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Section: Aromaticity and Antiaromaticitymentioning

confidence: 99%

Hydrogen bond design principles

Karas

Das

et al. 2020

WIREs Comput Mol Sci

103

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“…67 Presumably, this effect can be analysed theoretically. 68 The data for homodimers of a, h, and e will fit the observed correlation better if their gas-phase PA will be increased by 15 kJ/mol. Thus, the attenuation of the proton affinity for these homodimers is smaller than for similar species.…”

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confidence: 92%

NMR Study of Solvation Effect on the Geometry of Proton-Bound Homodimers of Increasing Size

et al. 2017

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Hydrogen bond geometries in the proton-bound homodimers of quinoline and acridine derivatives in an aprotic polar solution have been experimentally studied using H NMR at 120 K. The reported results show that an increase of the dielectric permittivity of the medium results in contraction of the N···N distance. The degree of contraction depends on the homodimer's size and its substituent-specific solvation features. Neither of these effects can be reproduced using conventional implicit solvent models employed in computational studies. In general, the N···N distance in the homodimers of pyridine, quinoline, and acridine derivatives decreases in the sequence gas phase> solid state > polar solvent.

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“…[14] Thep osition of the conformational equilibrium in these new balances enables measurement of the energy of the Hbond at the end of alinear chain of one,two,orthree Hbonds.These molecular balances were synthesized and found to exist in two conformational states on the NMR timescale at room temperature (see the Supporting Information for NMR spectra and minimized structures). Conformers were assigned using 2D NMR spectroscopy and the equilibrium constant K was determined by integration of the 19 FNMR peaks corresponding to each conformer. Thed ifference in the Gibbs energy between the conformers was determined using DG = ÀRT lnK.…”

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confidence: 99%

Strong Short‐Range Cooperativity in Hydrogen‐Bond Chains

et al. 2017

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Chains of hydrogen bonds such as those found in water and proteins are often presumed to be more stable than the sum of the individual H bonds. However, the energetics of cooperativity are complicated by solvent effects and the dynamics of intermolecular interactions, meaning that information on cooperativity typically is derived from theory or indirect structural data. Herein, we present direct measurements of energetic cooperativity in an experimental system in which the geometry and the number of H bonds in a chain were systematically controlled. Strikingly, we found that adding a second H‐bond donor to form a chain can almost double the strength of the terminal H bond, while further extensions have little effect. The experimental observations add weight to computations which have suggested that strong, but short‐range cooperative effects may occur in H‐bond chains.

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AMHB: (Anti)aromaticity-Modulated Hydrogen Bonding

Cited by 29 publications

References 66 publications

Hydrogen bond design principles

Hydrogen bond design principles

NMR Study of Solvation Effect on the Geometry of Proton-Bound Homodimers of Increasing Size

Strong Short‐Range Cooperativity in Hydrogen‐Bond Chains

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