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. We used SLG surfaces supported on copper, silicon carbide, and transparent fused silica (SiO(2)) substrates, enabling optical spectroscopy of COFs in transmission mode. Three chemically distinct COF films grown on SLG exhibit similar vertical alignment and long-range order, and two of these are of interest for organic electronic devices for which thin-film formation is a prerequisite for characterizing their optoelectronic properties.

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.

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. Complementary molecular dynamics and density functional theory calculations provide insight into the interlayer spacing of the COF and suggest that adjacent layers are horizontally offset by 1.7-1.8 Å, in contrast to the eclipsed AA stacking typically proposed for these materials.

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.

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Two‐dimensional covalent organic frameworks (COFs) are polymer networks that organize molecular building blocks into porous, layered structures of interest for organic optoelectronic and energy storage devices. Current synthetic methods produce these materials as either insoluble, microcrystalline powders or as oriented thin films on various substrates, including single‐layer graphene (SLG). Under these conditions, COF thin films form on both the graphene‐coated and bare regions of the substrate, suggesting uncontrolled nucleation processes that occur either in solution or nonselectively on different surfaces. Here, we describe modified polymerization conditions that provide COF films selectively on SLG. This finding enables COF films to be grown on lithographically patterned SLG substrates, which provide insight into the uniformity of film growth across the substrate and factors relevant to their nucleation and growth. The ability to grow COF films selectively on lithographically patterned SLG will facilitate their integration into devices. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 378–384

Hin zur Anwendung: Dünne Filme kovalenter organischer Gerüste (COFs) sind ideale Materialien für den vertikalen Ladungstransport und dienen als Vorstufen für geordnete Heterokontakte. Bisher jedoch waren die Poren solcher Materialien zu klein, um kontinuierliche Netzwerke komplementärer Elektronenakzeptoren beherbergen zu können. Vier Phthalocyanin‐COFs werden nun beschrieben, deren Porengröße in den mesoporösen Bereich reicht (siehe Beispiel).

In this work we have bridged the use of mild and living organocatalytic ring-opening polymerization to facilitate the synthesis of cross-linked networks with an emphasis on hydrogels. Amidine-catalyzed ring-opening polymerization of bis-carbonate macromonomers in the presence of an alcohol provides the onset for the reaction and various building blocks issued from the initiator, macromonomer and comonomer can be used in different proportions to tailor the swelling behavior and mechanical integrity of final networks. Easy modifications of the building blocks additionally allow for finely tuning the hydrogel functionality and/or promoting responsiveness in the final structure.