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. 2020 Nov-Dec;10(6):e1477.
doi: 10.1002/wcms.1477. Epub 2020 May 16.

Hydrogen bond design principles

Lucas J Karas  1 , Chia-Hua Wu  1 , Ranjita Das  1 , Judy I-Chia Wu  1
Affiliations

Hydrogen bond design principles

Lucas J Karas et al. Wiley Interdiscip Rev Comput Mol Sci. 2020 Nov-Dec.

Abstract

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.

Keywords: aromaticity; hydrogen bonding; resonance-assisted hydrogen bonding; secondary electrostatic interactions.

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Conflict of interest statement

CONFLICT OF INTEREST The authors declare no potential conflict of interest.

Figures

FIGURE 1
FIGURE 1
Timeline for the development of hydrogen bond design principles
FIGURE 2
FIGURE 2
Depictions of hydrogen bonding, in (a) H2OH2O and (b) ammonium hydroxide, based on the early works of Latimer and Rodebush
FIGURE 3
FIGURE 3
Effects of electronegativity on O—H…N vs. N—H…N hydrogen bond strength. Explanations based on: (a) donor–acceptor orbital interactions (using water…ammonia and ammonia…ammonia as examples), and (b) dipole–dipole interactions
FIGURE 4
FIGURE 4
(a) Schematic illustration of CH…Y interactions (Y = electronegative atom or anion). (b) F2C—H…O hydrogen bonding. (c) Examples of anion receptors based on C—H…anion interactions
FIGURE 5
FIGURE 5
(a) Schematic illustration of XH…π interactions. (b) and (c) Examples of OH…π hydrogen bonding. (d) Example of B—H…π hydrogen bonding
FIGURE 6
FIGURE 6
(a) Schematic illustration of dihydrogen bonding. Dihydrogen bonds were shown to direct the (b) preassembly of covalent materials, and (c) the diastereoselectivity of borohydride reduction
FIGURE 7
FIGURE 7
(a) The original “proton sponge,” DMAN. (b) Protonation of the diamine relieves lone pair repulsion, resulting in low-barrier [N…H…N]+ hydrogen bonding
FIGURE 8
FIGURE 8
Examples of other diamine-based proton sponges: TMGN, P2-TPPN, t-Bu–P2, vinamidine, and a fluorene-based proton sponge
FIGURE 9
FIGURE 9
Secondary electrostatic interactions (SEIs) between proton donors (“D,” in orange) and acceptors (“A,” in blue) in: (a) doubly, (b) triply, and (c) quadruply hydrogen bonded arrays. Solid lines indicate attractive interactions and dashed lines indicate repulsive interactions
FIGURE 10
FIGURE 10
Examples of quadruply hydrogen bonded arrays prepared based on the secondary electrostatic interaction (SEI) model. (a) 2-Ureido-4-pyrimidone, and (b) Blight’s AAAA-DDDD array
FIGURE 11
FIGURE 11
(a) Intramolecular and intermolecular resonance-assisted hydrogen bonding (RAHB) in β-diketone. (b) Possible RAHB effects in hydrogen-bonded dimers and base pairs
FIGURE 12
FIGURE 12
Resonance structures showing the effects of aromaticity gain in (a) tropolone, and in hydrogen-bonded (b) squaramide and C) guanine
FIGURE 13
FIGURE 13
(a) Aromaticity gain and loss in hydrogen-bonded heterocycles, and (b) a reversed effect in photoexcited states
FIGURE 14
FIGURE 14
(a) Hydrogen bonding networks in the active site of triosephosphate isomerase. (b) Cooperative hydrogen bonds can stabilize the conjugate base of OH substituted benzoic acid (note pKa values for the acid). (c) Example of a covalent polyol system. (d) Enhanced hydrogen bonding resulting from neutral, short-range networks (see OH group in bold)
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References

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