Supramolecular Main-Group Chemistry

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Synthetic chemists have achieved exquisite control of the structure of matter at atomic scale. Their ability to selectively form and rearrange bonds between atoms is behind spectacular advances in the development of new medicinal drugs and materials for advanced technologies, to name a couple of examples. However, manipulating strong interatomic bonds often leads to unwanted side processes; chemical reactions seldom are 100% efficient. Even when by-products are obtained in small amounts and are easily removed, the limited efficiencies of such methods are greatly amplified when a synthesis must be carried out in multiple steps in order to form a large and complex structure. In many instances nature gets around such a problem by using weak bonds, which are easy to break and reconnect; this property allows thermodynamics to spontaneously “correct errors” in the structure. The adaptation of this concept to the control of molecular organization and structure is the basis of supramolecular chemistry. Most work in this area has relied on intermolecular links like hydrogen bridges and the binding of metal ions to electron-rich molecules. In recent years, the affinity of atoms of elements like iodine for atoms bearing lone pairs of electrons has received much attention and the term “halogen bond” has formally been adopted by the International Union of Pure and Applied Chemistry to describe it. Other heavy elements, also from the p-block of the periodic table, have analogous abilities to form supramolecular links.