How strong is a hydrogen bond?
2485027#6
A hydrogen bond (H-bond), is a specific type of interaction that involves dipole-dipole attraction between a partially positive hydrogen atom and a highly electronegative, partially negative oxygen, nitrogen, sulfur, or fluorine atom (not covalently bound to said hydrogen atom). It is not a covalent bond, but instead is classified as a strong non-covalent interaction. It is responsible for why water is a liquid at room temperature and not a gas (given water's low molecular weight). Most commonly, the strength of hydrogen bonds lies between 0 - 4 kcal/mol, but can sometimes be as strong as 40 kcal/mol In solvents such as chloroform or carbontetrachloride one observes e.g. for the interaction between amides additive values of about 5 kJ/mol. According to L. Pauling the strength of a hydrogen bond is essentially determined by the electrostatic charges. Measurements of thousands complexes in chloroform or carbontetrachloride have led to additive free energy increments for all kind of donor-acceptor combinations.
Non-covalent interactions
13609#6
Hydrogen bonds can vary in strength from weak (1–2 kJ mol) to strong (161.5 kJ mol in the ion ). Typical enthalpies in vapor include:
Hydrogen bond
9821563#25
High hydrogen adsorption enthalpy is also important. Theoretical studies have shown that 22-25 kJ/mol interactions are ideal for hydrogen storage at room temperature, as they are strong enough to adsorb H, but weak enough to allow for quick desorption. The interaction between hydrogen and uncharged organic linkers is not this strong, and so a considerable amount of work has gone in synthesis of MOFs with exposed metal sites, to which hydrogen adsorbs with an enthalpy of 5-10 kJ/mol. Synthetically, this may be achieved by using ligands whose geometries prevent the metal from being fully coordinated, by removing volatile metal-bound solvent molecules over the course of synthesis, and by post-synthetic impregnation with additional metal cations. (CH)V(CO)(H) and Mo(CO)(H) are great examples of increased binding energy due to open metal coordination sites; however, their high metal-hydrogen bond dissociation energies result in a tremendous release of heat upon loading with hydrogen, which is not favorable for fuel cells. MOFs, therefore, should avoid orbital interactions that lead to such strong metal-hydrogen bonds and employ simple charge-induced dipole interactions, as demonstrated in Mn[(MnCl)(BTT)].
Metal–organic framework
7863793#5
A hydrogen bond is a specific dipole where a hydrogen atom has a partial positive charge (δ+) to due a neighboring electronegative atom or functional group. Hydrogen bonds are amongst the strong intermolecular interactions know other than ion-dipole interactions. For intermolecular hydrogen bonds the δ+ hydrogen interacts with a δ- on an adjacent molecule. Examples of molecular solids that hydrogen bond are water, amino acids, and acetic acid. For acetic acid, the hydrogen (δ+) on the alcohol moiety of the carboxylic acid hydrogen bonds with other the carbonyl moiety (δ-) of the carboxylic on the adjacent molecule. This hydrogen bond leads a string of acetic acid molecules hydrogen bonding to minimize free energy. These strings of acetic acid molecules then stack together to build solids.
Molecular solid
13609#7
The X−H distance is typically ≈110 pm, whereas the H···Y distance is ≈160 to 200 pm. The typical length of a hydrogen bond in water is 197 pm. The ideal bond angle depends on the nature of the hydrogen bond donor. The following hydrogen bond angles between a hydrofluoric acid donor and various acceptors have been determined experimentally:
Strong hydrogen bonds are revealed by downfield shifts in the H NMR spectrum. For example, the acidic proton in the enol tautomer of acetylacetone appears at δ15.5, which is about 10 ppm downfield of a conventional alcohol.
Hydrogen bond
3756#16
At room temperature, hydrogen bromide is a colourless gas, like all the hydrogen halides apart from hydrogen fluoride, since hydrogen cannot form strong hydrogen bonds to the large and only mildly electronegative bromine atom; however, weak hydrogen bonding is present in solid crystalline hydrogen bromide at low temperatures, similar to the hydrogen fluoride structure, before disorder begins to prevail as the temperature is raised. Aqueous hydrogen bromide is known as hydrobromic acid, which is a strong acid (p"K" = −9) because the hydrogen bonds to bromine are too weak to inhibit dissociation. The HBr/HO system also involves many hydrates HBr·"n"HO for "n" = 1, 2, 3, 4, and 6, which are essentially salts of bromine anions and hydronium cations. Hydrobromic acid forms an azeotrope with boiling point 124.3 °C at 47.63 g HBr per 100 g solution; thus hydrobromic acid cannot be concentrated beyond this point by distillation.
Bromine
1846298#5
Hydrogen bond-assisted supramolecular assembly is the process of assembling small organic molecules to form large supramolecular structures by non-covalent hydrogen bonding interactions. The directionality, reversibility, and strong bonding nature of hydrogen bond make it an attractive and useful approach in supramolecular assembly. Functional groups such as carboxylic acids, ureas, amines, and amides are commonly used to assemble higher order structures upon hydrogen bonding.
Supramolecular assembly
13609#31
Many polymers are strengthened by hydrogen bonds within and between the chains. Among the synthetic polymers, a well characterized example is nylon, where hydrogen bonds occur in the repeat unit and play a major role in crystallization of the material. The bonds occur between carbonyl and amine groups in the amide repeat unit. They effectively link adjacent chains, which help reinforce the material. The effect is great in aramid fibre, where hydrogen bonds stabilize the linear chains laterally. The chain axes are aligned along the fibre axis, making the fibres extremely stiff and strong.
Hydrogen bond
15417#5
A "hydrogen bond" is the attraction between the lone pair of an electronegative atom and a hydrogen atom that is bonded to either nitrogen, oxygen, or fluorine. The hydrogen bond is often described as a strong electrostatic dipole-dipole interaction. However, it also has some features of covalent bonding: it is directional, stronger than a van der Waals force interaction, produces interatomic distances shorter than the sum of van der Waals radius, and usually involves a limited number of interaction partners, which can be interpreted as a kind of valence.
Intermolecular force
13609#5
The hydrogen bond is often described as an electrostatic dipole-dipole interaction. However, it also has some features of covalent bonding: it is directional and strong, produces interatomic distances shorter than the sum of the van der Waals radii, and usually involves a limited number of interaction partners, which can be interpreted as a type of valence. These covalent features are more substantial when acceptors bind hydrogens from more electronegative donors.
Hydrogen bond