Construction and repair of highly ordered 2D covalent networks by chemical equilibrium regulation

Guan, Cui-Zhong; Wang, Dong; Li, Wan

doi:10.1039/c2cc16892h

Cited by 199 publications

(213 citation statements)

References 32 publications

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“…13 Up to day, UTNs have been prepared via a serials of approaches, such as the exfoliation of lamellar crystals, the self-assembly of molecules and the synthesis methods etc. [2][3][4][5][6][7][8][9][10][11] 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 4 LPCR is a kind of very important method to synthesize nanomaterials, and has been firstly applied by our group to synthesize size-and shape-controlled organic nanomaterials. [16][17] However, it is still a huge challenge to prepare UTNs formed via only weak interaction based on the method.…”

Section: And 3dmentioning

confidence: 98%

“…Since the appearance of graphene in 2004, 2 UTNs have gradually attracted wide attention of researcher because of their unique structure and fascinating physical and chemical properties. [2][3][4][5][6][7][8][9][10][11] At present, both 2D UTNs with single-atom or singlemolecule thickness and 3D UTNs are usually prepared via strong interactions. For example, 2D…”

mentioning

confidence: 99%

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Synthesis of Ultrathin Nanosheets of Perylene

Lai

Li²,

Pan³

et al. 2015

Crystal Growth & Design

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Here, we report f ree-standing nanosheets with the thickness of <10 nm (UTNs) formed via only weak π−π interaction and/or van der Waals force. In the work, morphology-controlled synthesis of an α-form perylene crystal are achieved by controlling its growth along the [001] direction in CTAB-assisted liquid-phase chemical reaction (LPCR). UTNs of perylene are prone to forming at low monomer chemical potential (μ) and short aging time, while thicker nanoflakes, even rods, tend to appear at high μ and long aging time due to destroyed CTAB selective adsorption on the (001) plane. Here, UTNs of perylene with thickness of about 1 nm can also be successfully synthesized. To the best of our knowledge, it is the thinnest organic UTNs formed through only weak intermolecular interactions so far. UV−vis absorption spectra show that the size effect of the crystal is closely associated with its orientation and/or shape. The effect of μ and aging time on the size and shape clearly reveals that the mechanism of formation of perylene UTNs is a CTAB-induced two-dimensional (2D) nucleation and layer-by-layer growth model, via which a facile path to synthesize UTNs is provided. The work is expected to promote the study and application of 2D nanocrystals of organic semiconductor.

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Section: And 3dmentioning

confidence: 98%

mentioning

confidence: 99%

Synthesis of Ultrathin Nanosheets of Perylene

Lai

Li²,

Pan³

et al. 2015

Crystal Growth & Design

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“…[28][29][30][31][32] These approaches, however, perform monomer assembly and polymerization simultaneously under dynamic-bond-forming conditions, and usually provide polymers with many defects and only short-range order. [33] A reversible reaction environment might improve the surface covalent organic frameworks (SCOF) quality, [34][35][36] but typically thermodynamic equilibrium conditions cannot be achieved in UHV.…”

Section: Introductionmentioning

confidence: 99%

Stereoselective Photopolymerization of Tetraphenylporphyrin Derivatives on Ag(110) at the Sub‐Monolayer Level

Basagni

Colazzo

Sedona

et al. 2014

Chemistry A European J

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We explore a photochemical approach to achieve an ordered polymeric structure at the sub-monolayer level on a metal substrate. In particular, a tetraphenylporphyrin derivative carrying para-amino-phenyl functional groups is used to obtain extended and highly ordered molecular wires on Ag(110). Scanning tunneling microscopy and density functional theory calculations reveal that porphyrin building blocks are joined through azo bridges, mainly as cis isomers. The observed highly stereoselective growth is the result of adsorbate/surface interactions, as indicated by X-ray photoelectron spectroscopy. At variance with previous studies, we tailor the formation of long-range ordered structures by the separate control of the surface molecular diffusion through sample heating, and of the reaction initiation through light absorption. This previously unreported approach shows that the photo-induced covalent stabilization of self-assembled molecular monolayers to obtain highly ordered surface covalent organic frameworks is viable by a careful choice of the precursors and reaction conditions.

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“…1b using a trivalent 1,3,5-triazine connecting group. 2D COFs can now be synthesized using dynamic covalent chemistry in milligram quantities 9 organic monomers, with solvothermal 10 , microwave 11,12 and ionothermal 13,14 synthesis in solution or directly as monolayers on metallic 15 and graphitic 16,17 substrates. Solution-based monoand few-layer sheets can now be produced at micron diameters, highly crystalline 18 and largely defect-free 19 .…”

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confidence: 99%

Dirac Cones in two-dimensional conjugated polymer networks

et al. 2014

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Linear electronic band dispersion and the associated Dirac physics has to date been limited to special-case materials, notably graphene and the surfaces of three-dimensional (3D) topological insulators. Here we report that it is possible to create two-dimensional fully conjugated polymer networks with corresponding conical valence and conduction bands and linear energy dispersion at the Fermi level. This is possible for a wide range of polymer types and connectors, resulting in a versatile new family of experimentally realisable materials with unique tuneable electronic properties. We demonstrate their stability on substrates and possibilities for doping and Dirac cone distortion. Notably, the cones can be maintained in 3D-layered crystals. Resembling covalent organic frameworks, these materials represent a potentially exciting new field combining the unique Dirac physics of graphene with the structural flexibility and design opportunities of organic-conjugated polymer chemistry.

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Construction and repair of highly ordered 2D covalent networks by chemical equilibrium regulation

Abstract: The construction of well-ordered 2D covalent networks via the dehydration of di-borate aromatic molecules was successfully realized through introducing a small amount of water into a closed reaction system to regulate the chemical equilibrium.

Cited by 199 publications

References 32 publications

Synthesis of Ultrathin Nanosheets of Perylene

Synthesis of Ultrathin Nanosheets of Perylene

Stereoselective Photopolymerization of Tetraphenylporphyrin Derivatives on Ag(110) at the Sub‐Monolayer Level

Dirac Cones in two-dimensional conjugated polymer networks

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