Driving Forces Controlling Host–Guest Recognition in Supercritical Carbon Dioxide Solvent

The formation of supramolecular host–guest complexes is a very useful and widely employed tool in chemistry. However, supramolecular chemistry in non‐conventional solvents such as supercritical carbon dioxide (scCO₂), one of the most promising sustainable solvents, is still in its infancy. In this work, we explored a successful route to the development of green processes in supercritical CO₂ by combining a theoretical approach with experiments. We were able to synthesize and characterize an inclusion complex between a polar aromatic molecule (benzoic acid) and peracetylated‐β‐cyclodextrin, which is soluble in the supercritical medium. This finding opens the way to wide, environmental friendly, applications of scCO₂ in many areas of chemistry, including supramolecular synthesis, reactivity and catalysis, micro and nano‐particle formation, molecular recognition, as well as enhanced extraction processes with increased selectivity.