Radical-pairing-induced molecular assembly and motion

Radical-pairing interactions between conjugated organic π-radicals are relative newcomers to the inventory of molecular recognition motifs explored in supramolecular chemistry. The unique electronic, magnetic, optical and redox-responsive properties of the conjugated π-radicals render molecules designed with radical-pairing interactions useful for applications in various areas of chemistry and materials science. In particular, the ability to control formation of radical cationic or anionic species, by redox stimulation, provides a flexible trigger for directed assembly and controlled molecular motions, as well as a convenient means of inputting energy to fuel non-equilibrium processes. In this Review, we provide an overview of different examples of radical-pairing-based recognition processes and of their emerging use in (1) supramolecular assembly, (2) templation of mechanically interlocked molecules, (3) stimuli-controlled molecular switches and, by incorporation of kinetic asymmetry in the design, (4) the creation of unidirectional molecular transporters based on pumping cassettes powered by fuelled switching of radical-pairing interactions. We conclude the discussion with an outlook on future directions for the field. Radical-pairing interactions were, until recently, considered something of a chemical curiosity. But these weak interactions, on par with hydrogen bonds, are easily switched on and off and, as a result, have become widely exploited in supramolecular chemistry, particularly in the assembly of out-of-equilibrium structures.