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.
doi:10.1038/nchem.2053
Flat is the question.
Full Text - 2D or not 2D? | PDF (538 KB) - 2D or not 2D?
See also: Article by Kory et al. | Article by Kissel et al. | News and Views by Champness | Interview with Benjamin King and Dieter Schlüter
doi:10.1038/nchem.2033
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.
Full Text - The chemists behind the crystals | PDF (1,069 KB) - The chemists behind the crystals
See also: Article by Kory et al. | Article by Kissel et al. | News and Views by Champness | Editorial
Neil R. Champness
doi:10.1038/nchem.2015
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.
Full Text - Two-dimensional materialsCrystallized creations in 2D | PDF (777 KB) - Two-dimensional materialsCrystallized creations in 2D
See also: Article by Kory et al. | Article by Kissel et al. | Interview with Benjamin King and Dieter Schlüter | Editorial
Patrick Kissel, Daniel J. Murray, William J. Wulftange, Vincent J. Catalano & Benjamin T. King
doi:10.1038/nchem.2008
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.
Abstract - A nanoporous two-dimensional polymer by single-crystal-to-single-crystal photopolymerization | Full Text - A nanoporous two-dimensional polymer by single-crystal-to-single-crystal photopolymerization | PDF (5,340 KB) - A nanoporous two-dimensional polymer by single-crystal-to-single-crystal photopolymerization | Supplementary information | Chemical compounds
See also: News and Views by Champness | Article by Kory et al. | Interview with Benjamin King and Dieter Schlüter | Editorial
Max J. Kory, Michael Wörle, Thomas Weber, Payam Payamyar, Stan W. van de Poll, Julia Dshemuchadse, Nils Trapp & A. Dieter Schlüter
doi:10.1038/nchem.2007
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.
Abstract - Gram-scale synthesis of two-dimensional polymer crystals and their structure analysis by X-ray diffraction | Full Text - Gram-scale synthesis of two-dimensional polymer crystals and their structure analysis by X-ray diffraction | PDF (4,534 KB) - Gram-scale synthesis of two-dimensional polymer crystals and their structure analysis by X-ray diffraction | Supplementary information | Chemical compounds
See also: News and Views by Champness | Article by Kissel et al. | Interview with Benjamin King and Dieter Schlüter | Editorial
Eric L. Spitler & William R. Dichtel
doi:10.1038/nchem.695
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
Abstract - Lewis acid-catalysed formation of two-dimensional phthalocyanine covalent organic frameworks | Full Text - Lewis acid-catalysed formation of two-dimensional phthalocyanine covalent organic frameworks | PDF (2,495 KB) - Lewis acid-catalysed formation of two-dimensional phthalocyanine covalent organic frameworks | Supplementary information | Chemical compounds
Subject terms: Materials chemistry | Organic chemistry
L. Lafferentz, V. Eberhardt, C. Dri, C. Africh, G. Comelli, F. Esch, S. Hecht & L. Grill
doi:10.1038/nchem.1242
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.
Abstract - Controlling on-surface polymerization by hierarchical and substrate-directed growth | Full Text - Controlling on-surface polymerization by hierarchical and substrate-directed growth | PDF (1,612 KB) - Controlling on-surface polymerization by hierarchical and substrate-directed growth | Supplementary information | Chemical compounds
Subject terms: Nanotechnology | Surface chemistry
See also: News and Views by Champness
Neil R. Champness
doi:10.1038/nchem.1276
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.
Full Text - Surface chemistryMaking the right connections | PDF (253 KB) - Surface chemistryMaking the right connections
Subject terms: Nanotechnology | Surface chemistry
See also: Article by Lafferentz et al.
Patrick Kissel, Rolf Erni, W. Bernd Schweizer, Marta D. Rossell, Benjamin T. King, Thomas Bauer, Stephan Götzinger, A. Dieter Schlüter & Junji Sakamoto
doi:10.1038/nchem.1265
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.
Abstract - Self-reproduction of supramolecular giant vesicles combined with the amplification of encapsulated DNA | Full Text - A two-dimensional polymer prepared by organic synthesis | PDF (4,433 KB) - A two-dimensional polymer prepared by organic synthesis | Supplementary information | Chemical compounds
Subject terms: Materials chemistry | Polymer chemistry | Synthesis
See also: News and Views by Uribe-Romo & Dichtel
Fernando J. Uribe-Romo & William R. Dichtel
doi:10.1038/nchem.1317
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.
Abstract - Two-dimensional materials: Polymers stripped down | Full Text - Two-dimensional materials: Polymers stripped down | PDF (412 KB) - Two-dimensional materials: Polymers stripped down
Subject terms: Materials chemistry | Polymer chemistry | Synthesis
See also: Article by Kissel et al.
John W. Colson & William R. Dichtel
doi:10.1038/nchem.1628
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.
Abstract - Rationally synthesized two-dimensional polymers | Full Text - Rationally synthesized two-dimensional polymers | PDF (3,657 KB) - Rationally synthesized two-dimensional polymers
Subject terms: Materials chemistry | Synthesis
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