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.

Lattice expansion of highly oriented 2D phthalocyanine covalent organic framework films.

Expanding into application: covalent organic framework (COF) films are ideally suited for vertical charge transport and serve as precursors of ordered heterojunctions. Their pores, however, were previously too small to accommodate continuous networks of complementary electron acceptors. Four phthalocyanine COFs with increased pore size well into the mesoporous regime are now described.

A 2D covalent organic framework with 4.7-nm pores and insight into its interlayer stacking.

Two-dimensional layered covalent organic frameworks (2D COFs) organize π-electron systems into ordered structures ideal for exciton and charge transport and exhibit permanent porosity available for subsequent functionalization. A 2D COF with the largest pores reported to date was synthesized by condensing 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) and 4,4'-diphenylbutadiynebis(boronic acid) (DPB). The COF was prepared as both a high surface area microcrystalline powder as well as a vertically oriented thin film on a transparent single-layer graphene/fused silica substrate.

Oriented 2D covalent organic framework thin films on single-layer graphene.

Covalent organic frameworks (COFs), in which molecular building blocks form robust microporous networks, are usually synthesized as insoluble and unprocessable powders. We have grown two-dimensional (2D) COF films on single-layer graphene (SLG) under operationally simple solvothermal conditions. The layered films stack normal to the SLG surface and show improved crystallinity compared with COF powders.