2D polymers

The properties of 2D materials, such as graphene, arise not only from their composition but also their sheet-like structures. Synthetic 2D polymers made from well-defined monomers promise to expand the range of such materials, but are very difficult to synthesize. A collection of articles in this Focus highlights some of the latest research in making and characterizing single-crystal synthetic 2D polymers, and also considers the challenges and potential for these materials in the future.



The chemists behind the crystals pp751 - 753


Benjamin King and Dieter Schlüter, the corresponding authors of two Articles in this issue that describe single-crystal characterization of two-dimensional polymers, talk to Nature Chemistry about the background, challenges and prospects of their work.

See also: Article by Kory et al. | Article by Kissel et al. | News and Views by Champness | Editorial


News and Views

Two-dimensional materials: Crystallized creations in 2D pp757 - 759

Neil R. Champness


Two reports demonstrate that with the right molecules and the right crystalline arrangement, it is not only possible to create two-dimensional crystals, but also to separate them into single-molecule-thick sheets — so-called two-dimensional polymers.

See also: Article by Kory et al. | Article by Kissel et al. | Interview with Benjamin King and Dieter Schlüter | Editorial



A nanoporous two-dimensional polymer by single-crystal-to-single-crystal photopolymerization pp774 - 778

Patrick Kissel, Daniel J. Murray, William J. Wulftange, Vincent J. Catalano & Benjamin T. King


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Two-dimensional synthetic polymers can be produced through solid-state topochemical polymerization, but achieving this through a single-crystal-to-single-crystal transformation has not yet been demonstrated. Now, a fluorinated Y-shaped monomer has been preorganized in a lamellar crystal, which goes through two successive single-crystal-to-single-crystal phototransformations to give a 2D polymer; single-crystal X-ray diffraction has been used to elucidate its structure.

See also: News and Views by Champness | Article by Kory et al. | Interview with Benjamin King and Dieter Schlüter | Editorial

Gram-scale synthesis of two-dimensional polymer crystals and their structure analysis by X-ray diffraction pp779 - 784

Max J. Kory, Michael Wörle, Thomas Weber, Payam Payamyar, Stan W. van de Poll, Julia Dshemuchadse, Nils Trapp & A. Dieter Schlüter


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Accessing synthetic two-dimensional polymers that are analogous to graphene is synthetically and analytically challenging. Now, single crystals of a simple-to-make monomer have been grown and then photopolymerized to form layered single crystals of covalently bonded two-dimensional polymer. Much like natural graphite, these crystals can be exfoliated to form thin sheets and single layers of the polymer.

See also: News and Views by Champness | Article by Kissel et al. | Interview with Benjamin King and Dieter Schlüter | Editorial


From the archives

Lewis acid-catalysed formation of two-dimensional phthalocyanine covalent organic frameworks pp672 - 677

Eric L. Spitler & William R. Dichtel


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Covalent organic frameworks (COFs) organize organic subunits into predictable and precise networks with long-range order. The limited generality of methods for COF synthesis has thus far precluded the incorporation of complex building blocks into these emerging materials. Now, a new Lewis acid-catalysed protocol for boronic ester formation provides a two-dimensional COF containing stacked phthalocyanine chromophores

Subject terms: Materials chemistry | Organic chemistry

Controlling on-surface polymerization by hierarchical and substrate-directed growth pp215 - 220

L. Lafferentz, V. Eberhardt, C. Dri, C. Africh, G. Comelli, F. Esch, S. Hecht & L. Grill


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The bottom-up construction of covalently linked molecular architectures on surfaces has recently been demonstrated, but only rather simple structures can be obtained in such one-step connection processes. A sequential approach has now been used to induce the selective connection of molecules with a programmed reactivity, enabling network formation with high selectivity.

Subject terms: Nanotechnology | Surface chemistry

See also: News and Views by Champness

Surface chemistry: Making the right connections pp149 - 150

Neil R. Champness


How do you create a molecular circuit board? Covalently coupling different molecules in a sequential manner in surface-based nanostructures opens up new possibilities and hopes for molecular electronics.

Subject terms: Nanotechnology | Surface chemistry

See also: Article by Lafferentz et al.

A two-dimensional polymer prepared by organic synthesis pp287 - 291

Patrick Kissel, Rolf Erni, W. Bernd Schweizer, Marta D. Rossell, Benjamin T. King, Thomas Bauer, Stephan Götzinger, A. Dieter Schlüter & Junji Sakamoto


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A two-dimensional polymer with internal periodicity has now been constructed. The procedure involves the rational molecular design of monomers, which first crystallize into a laminar lattice. A photo-induced polymerization then occurs laterally within each layer, and the resulting polymer crystals are subsequently delaminated into individual, free-standing two-dimensional polymers.

Subject terms: Materials chemistry | Polymer chemistry | Synthesis

See also: News and Views by Uribe-Romo & Dichtel

Two-dimensional materials: Polymers stripped down pp244 - 245

Fernando J. Uribe-Romo & William R. Dichtel


Two-dimensional polymers can serve to organize chemical functionality periodically over large areas, but their rational synthesis has remained limited. Now, a free-standing, single-layer polymer sheet has been prepared and isolated through a two-step procedure — a photochemical reaction within a layered organic crystal followed by exfoliation.

Subject terms: Materials chemistry | Polymer chemistry | Synthesis

See also: Article by Kissel et al.

Rationally synthesized two-dimensional polymers pp453 - 465

John W. Colson & William R. Dichtel


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Two-dimensional polymers, which exhibit periodic bonding in two orthogonal directions, offer mechanical, electronic and structural properties distinct from their linear or irregularly crosslinked polymer counterparts. Their potential is largely unexplored because versatile and controlled synthetic strategies are only now emerging. This Review describes recent developments in two-dimensional polymerization methods.

Subject terms: Materials chemistry | Synthesis

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