Home
This Title All WIREs
WIREs RSS Feed
How to cite this WIREs title:
WIREs Comput Mol Sci
Impact Factor: 16.778

Hydrogen bond design principles

Full article on Wiley Online Library:   HTML PDF

Can't access this content? Tell your librarian.

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. This article is categorized under: Structure and Mechanism > Molecular Structures Structure and Mechanism > Reaction Mechanisms and Catalysis
(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
[ Normal View | Magnified View ]
(a) Schematic illustration of XH…π interactions. (b) and (c) Examples of OH…π hydrogen bonding. (d) Example of BH…π hydrogen bonding
[ Normal View | Magnified View ]
(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
[ Normal View | Magnified View ]
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
[ Normal View | Magnified View ]
Depictions of hydrogen bonding, in (a) H2OH2O and (b) ammonium hydroxide, based on the early works of Latimer and Rodebush1
[ Normal View | Magnified View ]
Timeline for the development of hydrogen bond design principles
[ Normal View | Magnified View ]
(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)
[ Normal View | Magnified View ]
(a) Aromaticity gain and loss in hydrogen‐bonded heterocycles, and (b) a reversed effect in photoexcited states
[ Normal View | Magnified View ]
Resonance structures showing the effects of aromaticity gain in (a) tropolone, and in hydrogen‐bonded (b) squaramide and C) guanine
[ Normal View | Magnified View ]
(a) Intramolecular and intermolecular resonance‐assisted hydrogen bonding (RAHB) in β‐diketone. (b) Possible RAHB effects in hydrogen‐bonded dimers and base pairs
[ Normal View | Magnified View ]
Examples of quadruply hydrogen bonded arrays prepared based on the secondary electrostatic interaction (SEI) model. (a) 2‐Ureido‐4‐pyrimidone,67 and (b) Blight's AAAA‐DDDD array68
[ Normal View | Magnified View ]
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
[ Normal View | Magnified View ]
Examples of other diamine‐based proton sponges: TMGN, P2‐TPPN, t‐Bu–P2, vinamidine, and a fluorene‐based proton sponge
[ Normal View | Magnified View ]
(a) The original “proton sponge,” DMAN. (b) Protonation of the diamine relieves lone pair repulsion, resulting in low‐barrier [N…H…N]+ hydrogen bonding
[ Normal View | Magnified View ]

Browse by Topic

Structure and Mechanism > Reaction Mechanisms and Catalysis
Structure and Mechanism > Molecular Structures

Access to this WIREs title is by subscription only.

Recommend to Your
Librarian Now!

The latest WIREs articles in your inbox

Sign Up for Article Alerts