Rationally synthesized two-dimensional polymers.

Synthetic polymers exhibit diverse and useful properties and influence most aspects of modern life. Many polymerization methods provide linear or branched macromolecules, frequently with outstanding functional-group tolerance and molecular weight control. In contrast, extending polymerization strategies to two-dimensional periodic structures is in its infancy, and successful examples have emerged only recently through molecular framework, surface science and crystal engineering approaches. In this Review, we describe successful 2D polymerization strategies, as well as seminal research that inspired their development. These methods include the synthesis of 2D covalent organic frameworks as layered crystals and thin films, surface-mediated polymerization of polyfunctional monomers, and solid-state topochemical polymerizations. Early application targets of 2D polymers include gas separation and storage, optoelectronic devices and membranes, each of which might benefit from predictable long-range molecular organization inherent to this macromolecular architecture.