Constraining molecules at the closest approach: chemistry at high pressure

The purpose of this tutorial review is to illustrate the effects that the application of high pressures can have on chemical reactions involving highly compressible molecular materials. The essentials of the high-pressure technology (generation and in situ control of high pressures) are described with particular attention to the versatile diamond anvil cell (DAC) apparatus. The general effects of pressure on chemical equilibrium, reaction rate and reaction mechanism are discussed. The motivation for application of high-pressure methods (in the 1-300 MPa range) to chemical synthesis and in biochemistry are illustrated focusing the attention on environmental effects and with an excursus on developing biotechnological applications. The peculiarities and the unexpected outcomes of chemical reactions occurring at very high pressures (>or=300 MPa) are discussed considering the extraordinary results obtained in polymerization and amorphization of simple molecules and of unsaturated hydrocarbons. The possible connection of the high temperature-high pressure thresholds for chemical reactions with microscopic counterparts (intermolecular distances, molecular orientations) is also discussed.