Mechanochemical preparation of molecular and supramolecular organometallic materials and coordination networks.

This Dalton Perspective deals with solvent-free reactions taking place within solids or between solids or involving a solid and a vapour. The focus is on reactions involving organometallic and coordination compounds and occurring via reassembling of non-covalent bonding, e.g. hydrogen bonds, and/or formation of ligand-metal coordination bonds. It is argued that reactions activated by mechanical mixing of solid reactants as well as those obtained by exposing a crystalline solid to a vapour can be exploited to "make crystals", which is the quintessence of crystal engineering. It is demonstrated through a number of examples that solvent-free methods, such as co-grinding, kneading, milling of molecular solids, or reactions of solid with vapours represent viable alternative, when not unique, routes for the preparation of novel molecular and supramolecular solids as well as for the preparation of polymorphic or solvate modifications of a same species. The structural characterization of the products requires the preparation of single crystals suitable for X-ray diffraction, a goal often achieved by seeding.