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.

共轭有机 π 自由基之间的自由基配对相互作用是超分子化学中探索的分子识别基序清单的相对较新的事物。共轭 π 自由基独特的电子、磁性、光学和氧化还原响应特性使设计的具有自由基配对相互作用的分子可用于化学和材料科学的各个领域。特别是，通过氧化还原刺激控制自​​由基阳离子或阴离子物种形成的能力，为定向组装和受控分子运动提供了灵活的触发，以及为非平衡过程提供燃料的输入能量的便捷方式。在本综述中，我们概述了基于自由基配对的识别过程的不同示例及其在 (1) 超分子组装中的新兴用途，(2) 机械互锁分子的模板，(3) 刺激控制的分子开关，以及通过在设计中结合动力学不对称性，(4) 基于泵送盒的单向分子转运体的创建，泵送盒由自由基配对相互作用的燃料切换提供动力. 我们以对该领域未来发展方向的展望来结束讨论。