Efficient cycloaddition of arynes to carbon nanotubes under microwave irradiation

Criado, Alejandro; Vizuete, María; Gómez‐Escalonilla, María J.; García-Rodríguez, Sergio; Fierro, J.L.G.; Cobas, Agustín; Peña, Diego; Guitián, Enrique; Langa, Fernando

doi:10.1016/j.carbon.2013.06.064

Cited by 26 publications

(28 citation statements)

References 40 publications

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“…Pyrazolinefunctionalized graphene hybrids 3a-d were prepared in a one-pot procedure from hydrazones 1a-d and NCS in the presence of NEt 3 and these were reacted with EG for 6 days at 170 1C (Scheme 1, bottom). 16,68 Microwave heating methods have emerged as an interesting alternative in fullerene, 69 carbon nanotube 70 and graphene chemistry; 71 therefore, this source of energy was used in these reactions and the reaction time was reduced to 1 hour.…”

Section: Experimental Demonstrationmentioning

confidence: 99%

Modulation of the exfoliated graphene work function through cycloaddition of nitrile imines

Barrejón

Gómez‐Escalonilla

Fierro

et al. 2016

Phys. Chem. Chem. Phys.

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After the feasibility of the 1,3-dipolar cycloaddition reaction between nitrile imines and exfoliated graphene by density functional theory calculations was proved, very few-layer graphene was effectively functionalized using this procedure. Hydrazones with different electronic properties were used as precursors for the 1,3-dipoles, and microwave irradiation as an energy source enabled the reaction to be performed in a few minutes. The anchoring of organic addends on the graphene surface was confirmed by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis.Ultraviolet photoelectron spectroscopy (UPS) was used to measure the work function and band gap of these new hybrids. Our results demonstrate that it is possible to modulate these important electronic valence band parameters by tailoring the electron richness of the organic addends and/or the degree of functionalization.

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Section: Experimental Demonstrationmentioning

confidence: 99%

Modulation of the exfoliated graphene work function through cycloaddition of nitrile imines

Barrejón

Gómez‐Escalonilla

Fierro

et al. 2016

Phys. Chem. Chem. Phys.

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“…[3][4][5][6] Covalent functionalization possibility of formation of both [2+2] and [4+2] reaction products. 19,23 The studies of Denis and Iribarne, 22 Criado et al, 19 and Yang et al 23 were performed using different computational methods, which made it difficult to compare the calculated properties of graphene and CNTs functionalized with benzyne. Furthermore, in the calculations of Criado et al…”

Section: Introductionmentioning

confidence: 99%

First-Principles Study of Graphene and Carbon Nanotubes Functionalized with Benzyne

Hammouri

Jha

2015

J. Phys. Chem. C

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We applied ab initio computational methods based on density functional theory to study the properties of graphene and single-walled carbon nanotubes functionalized with benzyne. The calculations were carried out using the SIESTA electronic structure code combined with the generalized gradient approximation for the exchange correlation functional. Our study showed that the reaction of cycloaddition of benzyne to pristine graphene was exothermic with the possibility of formation of both [2 + 2] and [4 + 2] reaction products. The binding energies of benzyne molecules attached to semiconducting zigzag and metallic armchair nanotubes were found to be inversely proportional to the nanotube diameter. The linear fits of the binding energies between benzyne and carbon nanotubes extrapolated to the zero curvature limit were in good agreement with the binding energies of benzyne attached to graphene. Our calculations demonstrated that the cycloaddition of benzyne could open up a nonzero gap between the valence and conduction bands of graphene and metallic carbon nanotubes. The value of the band gap was significantly affected by the geometry of benzyne attachment and by the choice of the supercell.

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“…When generated in the presence of appropriate reaction partners, they undergo a variety of chemical transformations that enable a plethora of applications in synthesis [5][6][7][8] . Recent examples include the construction of very large polycyclic aromatic hydrocarbons 9,10 , the use of pyridynes as building blocks 11 or the chemical modification of graphene sheets 12 and carbon nanotubes 13 . Moreover, recent approaches to generate benzynes by cycloisomerization of triyne precursors revealed unexpected opportunities in aryne chemistry [14][15][16][17] .…”

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confidence: 99%

On-surface generation and imaging of arynes by atomic force microscopy

et al. 2015

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Reactive intermediates are involved in many chemical transformations. However, their characterization is a great challenge because of their short lifetimes and high reactivities. Arynes, formally derived from arenes by the removal of two hydrogen atoms from adjacent carbon atoms, are prominent reactive intermediates that have been hypothesized for more than a century. Their rich chemistry enables a widespread use in synthetic chemistry, as they are advantageous building blocks for the construction of polycyclic compounds that contain aromatic rings. Here, we demonstrate the generation and characterization of individual polycyclic aryne molecules on an ultrathin insulating film by means of low-temperature scanning tunnelling microscopy and atomic force microscopy. Bond-order analysis suggests that a cumulene resonance structure is the dominant one, and the aryne reactivity is preserved at cryogenic temperatures. Our results provide important insights into the chemistry of these elusive intermediates and their potential application in the field of on-surface synthesis.

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Efficient cycloaddition of arynes to carbon nanotubes under microwave irradiation

Cited by 26 publications

References 40 publications

Modulation of the exfoliated graphene work function through cycloaddition of nitrile imines

Modulation of the exfoliated graphene work function through cycloaddition of nitrile imines

First-Principles Study of Graphene and Carbon Nanotubes Functionalized with Benzyne

On-surface generation and imaging of arynes by atomic force microscopy

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