The hydrogen bond is the most important of all directional intermolecular interactions. It is operative in determining molecular conformation, molecular aggregation, and the function of a vast number of chemical systems ranging from inorganic to biological. Research into hydrogen bonds experienced a stagnant period in the 1980s, but re-opened around 1990, and has been in rapid development since then. In terms of modern concepts, the hydrogen bond is understood as a very broad phenomenon, and it is accepted that there are open borders to other effects. There are dozens of different types of X-H.A hydrogen bonds that occur commonly in the condensed phases, and in addition there are innumerable less common ones. Dissociation energies span more than two orders of magnitude (about 0.2-40 kcal mol(-1)). Within this range, the nature of the interaction is not constant, but its electrostatic, covalent, and dispersion contributions vary in their relative weights. The hydrogen bond has broad transition regions that merge continuously with the covalent bond, the van der Waals interaction, the ionic interaction, and also the cation-pi interaction. All hydrogen bonds can be considered as incipient proton transfer reactions, and for strong hydrogen bonds, this reaction can be in a very advanced state. In this review, a coherent survey is given on all these matters.

The hydrogen bond in the solid state.

The halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. In this fairly extensive review, after a brief history of the interaction, we will provide the reader with a snapshot of where the research on the halogen bond is now, and, perhaps, where it is going. The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design.

The Halogen Bond

The hydrogen bond (HB) basicity of a series of ylides containing nitrogen, oxygen, or carbon as heavy atoms, as well as the influence of the formation of the HB complexes on their structure, has been studied. In addition, in this paper we propose the formation of some rather strong HBs (that could be considered low-barrier hydrogen bonds, LBHBs) between ylides and different neutral molecules. The ylides chosen for the study were H3N+−N-H, Me3N+−N-H, H2O+−N-H, Me2O+−N-H, H2O+−O-, Me2O+−O-, and Me3N+−C-H2. As HB donors, classical donors such as HF, HCN, and HCCH were used. The analysis of the protonation energies of the ylides and the optimized geometries, interaction energies, and characteristics of the electron density of the complexes shows that these ylides are very good HB acceptors, forming stable complexes even with weak HB donors. With strong donors, when the proton transfer did not take place, very strong HBs were formed with quite large interaction energies and very short HB distances which could ...

Behavior of Ylides Containing N, O, and C Atoms as Hydrogen Bond Acceptors

Hydrogen bonding is an important interaction playing a key role in chemical, physical, and biochemical processes. One can mention numerous examples such as the role of hydrogen bonding in enzymatic catalysis, arrangement of molecules in crystals, crystal engineering, proton transfer reactions, and also its important role in life processes. Hence, its nature is often the subject of investigations and polemics. One of the first definitions of hydrogen bonding was formulated by Pauling who stated that “under certain conditions an atom of hydrogen is attracted by rather strong forces to two atoms, instead of only one, so that it may be considered to be acting as a bond between them. This is called the hydrogen bond”. Pauling also pointed out that the hydrogen atom is situated only between the most electronegative atoms and it usually interacts much stronger with one of them. The latter interaction is a typical covalent bond (A-H). The interaction between hydrogen and another electronegative atom is much weaker and mostly electrostatic in nature; it is a nonbonding interaction (H 3 3 3B). This system is often designated as AH 3 3 3B where the B-center (acceptor of proton) should possess at least one lone electron pair; A-H is called the protondonating bond. Pauling stated that sometimes the H 3 3 3B interaction possesses characteristics of the covalent bond. The [FHF] ion is an example where the proton is inserted between two negative fluorine ions, accurately in the middle of the F 3 3 3 F distance. Hence, both H 3 3 3 F interactions are equivalent. This is in line with an early conclusion of Lewis that “an atom of hydrogen may at times be attached to two electron pairs of two different atoms” and with the statement of Latimer and Rodebush that “the hydrogen nucleus held by two octets constitutes a weak bond”. The latter statements correspond to recent studies on proton bound homodimers, that is, systems where the proton is inserted between two closed-shell moieties and where it often interacts equivalently with both of them. Chan and co-workers analyzed recently what factors determine whether the protonbound homodimer has a symmetric or an asymmetric hydrogen bond. In the other study, it is discussed what conditions should be fulfilled for the proton situated accurately in the midpoint of the donor-acceptor distance. The high level calculations up to CCSD(T)/6-311þþ(3df,3pd)//CCSD/6-311þþ(3df,3pd) were performed on the [FHF] ion and systems with O-H 3 3 3O or N-H 3 3 3N hydrogen bonds. The latter study is supported by the experimental X-ray and neutron diffraction data because there are numerous crystal structures with short O-H 3 3 3O hydrogen bonds and the proton situated in the central position or nearly so. Also recently, homogeneous and heterogeneous short and strong hydrogen bonds (SSHBs) as well as the proton bound homodimers were analyzed theoretically at MP2/aug-ccpVDZ þ diffuse(2s,2p) level. Among various topics, the matter was raised if hydrogen bonding is an electrostatic or covalent interaction. The following question arises: what does the covalency of hydrogen bonding mean? The decomposition of the interaction energy is useful to analyze hydrogen bonding and particularly to answer the latter question. One of the first decomposition schemes introduced is one of Morokuma and Kitaura, where the interaction energy is calculated within the Hartree-Fock one-electron approximation and it is decomposed into the following components: the exchange energy, EEX (arising from repulsive forces), and the other components, which might be a result of attractive forces: the polarization energy, EPL, the charge transfer energy, ECT, and the electrostatic energy, EES. If a method is applied where the correlation of electrons is taken into account, then the correlation energy may be included. One of the most important attractive components of the correlation energy is the dispersive energy. Different H-bonded systems were analyzed early by Umeyama and Morokuma who stated that: “The energy components are strongly distance dependent. At a relatively small separation, ES, CT, and PL can all be important attractive components, competing against a large EX repulsion. At larger distances for the same complex the short-range attractions CT and PL are usually unimportant and ES is the only important attraction.” One can see that the “covalency of interaction”may be connected with short H 3 3 3B distances where terms other than the electrostatic attractive one are important.

What is the covalency of hydrogen bonding

Supramolecular chemistry has expanded dramatically in recent years both in terms of potential applications and in its relevance to analogous biological systems. The formation and function of supramolecular complexes occur through a multiplicity of often difficult to differentiate noncovalent forces. The aim of this Review is to describe the crucial interaction mechanisms in context, and thus classify the entire subject. In most cases, organic host-guest complexes have been selected as examples, but biologically relevant problems are also considered. An understanding and quantification of intermolecular interactions is of importance both for the rational planning of new supramolecular systems, including intelligent materials, as well as for developing new biologically active agents.

Binding Mechanisms in Supramolecular Complexes

Hydrogen bonds (HBs) are the most important ‘weak’ interactions encountered in solid, liquid and gas phases. The HB can be defined as an attractive interaction between two molecular moieties in which at least one of them contains a hydrogen atom that plays a fundamental role. Classical HBs correspond to those formed by two heteroatoms, A and B, with a hydrogen atom bonded to one of them and located approximately in between (A–H···B). Recently, knowledge of the number of functional groups which act as hydrogen bond donors or acceptors has increased considerably and most of these new groups are discussed.

Non-conventional hydrogen bonds

The nature of bifurcated or three-centered hydrogen bonds (HB) has been investigated. Different families of compounds were chosen:  monomers with intramolecular three-centered HB, dimers with a HB donor (HBD) and a molecule with two HB acceptor (HBA) groups, and trimers with one HBD and two HBAs. All the systems were optimized at the B3LYP/6-31G* level, and, in the case of the complexes, the interaction energies were evaluated and corrected with the basis set superposition error (BSSE). The electronic nature of these three-centered HBs was analyzed by means of the atoms in molecules (AIM) approach. The present study indicates the existence of bifurcated bond paths in the AIM analysis with electron densities that can be classified as follows:  (i) compounds with symmetric three-centered HBs presenting two symmetric bond critical points with equal values of electron density; (ii) compounds with asymmetric three-centered HBs presenting two bond critical points with different values of electron density; (iii)...

Bifurcated Hydrogen Bonds: Three-Centered Interactions

A theoretical study of the linear and multiple approximation in a series of complexes formed by molecules with electron-rich hydrogen atoms has been carried out. The interaction energy (taking into account the zero-point energy and the basis set superposition error), the atomic charges, and the electron density of the monomers and complexes have been evaluated at the MP2/6-311++G** level. The linear complexes, which show a strong similarity to the standard hydrogen bonds except for the reverse direction of the electron transfer, could be defined as inverse hydrogen bonds.

Inverse Hydrogen-Bonded Complexes

The present review summarizes the information available on the ab initio calculations of spin-spin nuclear coupling constants through hydrogen bonds or in van der Waals complexes. It also reports the sources of experimental data on nhJXY scalar couplings.

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José Elguero

Papers

Non-conventional hydrogen bonds

Bifurcated Hydrogen Bonds: Three-Centered Interactions

Inverse Hydrogen-Bonded Complexes

Review on DFT and ab initio Calculations of Scalar Coupling Constants

Non-Conventional Hydrogen Bonds