Dimerization of Conjugated Radical Cations: An Emerging Non‐Covalent Interaction for Self‐Assembly

Aromatic stacking has played a significant role in the design of discrete supramolecular systems. However, for many years, the stacking of conjugated radical cations has been considered only as a novelty due to its weakness. In recent years, it has been demonstrated that the stacking of conjugated radical cations, particularly those formed by bipyridinium or tetrathiafulvalene, can be enhanced remarkably when they are incorporated into rationally designed, preorganized frameworks or entrapped into a confined space. This Focus Review highlights the recent advance in its application as an emerging non-covalent force for the construction of various supramolecular structures.