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Journal ArticleDOI

The hydrogen bond in the solid state.

Thomas Steiner
- 04 Jan 2002 - 
- Vol. 41, Iss: 1, pp 48-76
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TLDR
The hydrogen bond is the most important of all directional intermolecular interactions, operative in determining molecular conformation, molecular aggregation, and the function of a vast number of chemical systems ranging from inorganic to biological.
Abstract
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.

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Citations
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Journal ArticleDOI

Fingerprinting intermolecular interactions in molecular crystals

TL;DR: In this paper, a two-dimensional mapping of the Hirshfeld surfaces of a molecular molecule is presented, which summarizes quantitatively the nature and type of intermolecular interaction experienced by a molecule in the bulk, and presents it in a convenient graphical format.
Journal ArticleDOI

Proton-Coupled Electron Transfer

TL;DR: Proton-coupled electron transfer is an important mechanism for charge transfer in a wide variety of systems including biology- and materials-oriented venues and several are reviewed.
Journal ArticleDOI

Novel tools for visualizing and exploring intermolecular interactions in molecular crystals.

TL;DR: A new way of exploring packing modes and intermolecular interactions in molecular crystals is described, using Hirshfeld surfaces to partition crystal space, using identifiable patterns of interaction between small molecules to rationalize the often complex mix of interactions displayed by large molecules.
Journal ArticleDOI

Asymmetric catalysis by chiral hydrogen-bond donors.

TL;DR: This review documents the structural and mechanistic features that contribute to high enantioselectivity in hydrogen-bond-mediated catalytic processes in small-molecule, synthetic catalyst systems.
References
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Journal ArticleDOI

The H-index unambiguously discriminates between hydrogen bonding and improper blue-shifting hydrogen bonding

TL;DR: Hobza and Havlas as discussed by the authors showed that X-H···Y contacts can also be characterised by a blue shift of the X−H stretch frequency, which is called blue-shifting H-bonding.
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Visualization and characterization of non-covalent networks in molecular crystals: automated assignment of graph-set descriptors for asymmetric molecules.

TL;DR: A method of visualizing intermolecular networks (for example, hydrogen-bonded networks) in the crystalline state has been developed, based on the concept of link atoms, enabling the generation and investigation of extended networks.
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Fluoride ligands exhibit marked departures from the hydrogen bond acceptor behavior of their heavier halogen congeners

TL;DR: In this article, the viability of hydrogen bonding is clearly established for all donor-acceptor combinations, D−H···X-M (D=C, N, O; X=F, Cl, Br, I).
Journal ArticleDOI

Inverse Hydrogen-Bonded Complexes

TL;DR: In this paper, 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, where 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.
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