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

Solid state hydrolysis of acetylanthranyl Assistance by hydrogen bonding

Solid-state chemistry of organic polyvalent iodine compounds. VII. The relationships between crystal packing modes, solid-state intermolecular interactions, and infrared spectra of benzoxiodole compounds☆

Growth of High-Quality Crystals Containing Peptides: Arenesulfonate Salts of L-Alanyl-L-Alanine, Glycylglycine, and L-Leucyl-L-Alanine

Phenylazophenylpalladium hexafluoroacetyl-acetonate can be grown from solution in a yellow or red polymorphic form. The yellow form undergoes a thermal polymorphic transformation to the red form which is accompanied by a sudden discontinuous crystal expansion of 10% of the length of the crystal. The packing patterns of the two crystal forms, as determined by crystal structure analysis, show that the expansion may result from a slip mechanism similar to a Martensitic transformation. The color change is probably due to the rotation of the exocyclic phenyl ring into the plane of the phenylazo group. It remains a puzzle why the expansion is so abrupt and why the color change takes place after the expansion in an independent process.

Margaret C. Etter

Papers

Solid state hydrolysis of acetylanthranyl Assistance by hydrogen bonding

Solid-state chemistry of organic polyvalent iodine compounds. VII. The relationships between crystal packing modes, solid-state intermolecular interactions, and infrared spectra of benzoxiodole compounds☆

Growth of High-Quality Crystals Containing Peptides: Arenesulfonate Salts of L-Alanyl-L-Alanine, Glycylglycine, and L-Leucyl-L-Alanine

Crystal Expansion During a Thermochromic Transformation

Crystal and molecular studies of succinimide-lithium salt complexes