From molecules to crystal engineering: supramolecular isomerism and polymorphism in network solids.

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.

Encoding and decoding hydrogen-bond patterns of organic compounds

Molecular self-assembly is the spontaneous association of molecules under equilibrium conditions into stable, structurally well-defined aggregates joined by noncovalent bonds. Molecular self-assembly is ubiquitous in biological systems and underlies the formation of a wide variety of complex biological structures. Understanding self-assembly and the associated noncovalent interactions that connect complementary interacting molecular surfaces in biological aggregates is a central concern in structural biochemistry. Self-assembly is also emerging as a new strategy in chemical synthesis, with the potential of generating nonbiological structures with dimensions of 1 to 10(2) nanometers (with molecular weights of 10(4) to 10(10) daltons). Structures in the upper part of this range of sizes are presently inaccessible through chemical synthesis, and the ability to prepare them would open a route to structures comparable in size (and perhaps complementary in function) to those that can be prepared by microlithography and other techniques of microfabrication.

https://science.sciencemag.org/content/sci/254/5036/1312.full.pdf

Molecular self-assembly and nanochemistry: a chemical strategy for the synthesis of nanostructures.

Molecular self-assembly and nanochemistry: A chemical strategy for the synthesis of nanostructures

A method is presented based on graph theory for categorizing hydrogen-bond motifs in such a way that complex hydrogen-bond patterns can be disentangled, or decoded, systematically and consistently. This method is based on viewing hydrogen-bond patterns topologically as if they were intertwined nets with molecules as the nodes and hydrogen bonds as the lines. Surprisingly, very few parameters are needed to define the hydrogen-bond motifs comprising these networks. The methods for making these assignments, and examples of their chemical utility are given.

Graph-set analysis of hydrogen-bond patterns in organic crystals

Hydrogen bond-directed cocrystallization and molecular recognition properties of diarylureas

Single crystal X-ray structures of a series of guanidinium alkane- and arensulfonates C(NH 2 ) 3 + RSO 3 - (R=(CH 2 ) x CH 3 (x=0-3), (1S)-(+)-10-camphor, benzene, 1-naphthalene, and 2-naphthalene) reveal self-assembly of the ions into unique two-dimensional hydrogen-bonded sheets directed by hydrogen bonds betwen the six guanidinium protons and the six lone electron pairts of the sulfonate oxygen atoms. The sheets assemble in the third dimension as either single layers or bilayers with interpenetrating R groups, depending upon the steric requirements of the R groups

Margaret C. Etter

Papers

Encoding and decoding hydrogen-bond patterns of organic compounds

Graph-set analysis of hydrogen-bond patterns in organic crystals

Hydrogen bond-directed cocrystallization and molecular recognition properties of diarylureas

Layered Materials by Molecular Design: Structural Enforcement by Hydrogen Bonding in Guanidinium Alkane- and Arenesulfonates

Hydrogen-bond formation in nitroanilines: the first step in designing acentric materials