Recent highlights in hemicarcerand chemistry

Since Donald J. Cram's first synthesis of a carcerand, which permanently en trapped a single guest molecule, many other carcerands and hemicarcerands h ave been synthesized and studied. Slowly, we begin to understand the role o f the template in the formation of hemicarceplexes and carceplexes, why som e hemi carceplexes are more stable than others, and how guests enter and ex it the inner phases of molecular containers. In this Account we discuss our new insight in the chemistry of molecular containers, as well as recent hi ghlights in through-shell chemistry and in the inner-phase stabilization of reactive intermediates.