Azafullerenes Encapsulated within Single-Walled Carbon Nanotubes

Pagona, Georgia; Rotas, Georgios; Khlobystov, Andrei N.; Chamberlain, Thomas W.; Porfyrakis, Kyriakos; Tagmatarchis, Nikos

doi:10.1021/ja800760w

Cited by 50 publications

(45 citation statements)

References 19 publications

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“…This demonstrates a remarkable property of carbon nanotubes to act not only as nanoreactors constraining the space around the chemical reaction and templating the formation of nanoclusters or the growth of nanoribbons, but also as electrically active host-structures lending their electrons when they are required for a chemical reaction to occur inside SWNT, and retrieving electrons back when they are no longer required by the guest-species. In summary, carbon nanotubes are becoming an increasingly important class of nanoscale containers and reactors, where the pathways of chemical reactions can change significantly as a result of the restricted space of the reaction [5][6][7][8][9][10][11][12][13][14][15][16][17], or due to the interactions between the reactant molecules or catalyst particles with the host-nanotube [23,24]. Being highly conducting and having a symmetric distribution of filled and empty electronic states, SWNT possess remarkable electric properties and a unique ability to donate or accept electrons, which make nanotubes distinct among other nanocontainers and nanoreactors.…”

Section: Equationmentioning

confidence: 99%

Carbon Nanotubes as Electrically Active Nanoreactors for Multi-Step Inorganic Synthesis: Sequential Transformations of Molecules to Nanoclusters and Nanoclusters to Nanoribbons

et al. 2016

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In organic synthesis, the composition and structure of products are predetermined by the reaction conditions; however, the synthesis of well-defined inorganic nanostructures often presents a significant challenge yielding non-stoichiometric or polymorphic products. In this study, confinement in the nanoscale cavities of single-walled carbon nanotubes (SWNT) provides a new approach for multi-step inorganic synthesis where sequential chemical transformations take place within the same nanotube. In the first step, SWNT donate electrons to the reactant iodine molecules (I2) transforming them to iodide anions (I -). These then react with metal hexacarbonyls (M(CO)6, M = Mo or W) in the next step yielding anionic nanoclusters [M6I14] 2-, the size and composition of which are strictly dictated by the nanotube cavity, as demonstrated by aberration corrected high resolution transmission electron microscopy (AC-HRTEM), scanning transmission electron microscopy (STEM) and energy dispersive X-ray (EDX) spectroscopy. Atoms in the nanoclusters [M6I14] 2-are arranged in a perfect octahedral geometry and can engage in further chemical reactions within the nanotube, either reacting with each other leading to a new polymeric phase of molybdenum iodide [Mo6I12]n, or with hydrogen sulphide gas giving rise to nanoribbons of molybdenum/tungsten disulphide [MS2]n in the third step of the synthesis. Electron microscopy measurements demonstrate that the products of the multi-step inorganic transformations are precisely controlled by the SWNT nanoreactor, with complementary Raman spectroscopy revealing the remarkable property of SWNT to act as a reservoir of electrons during the chemical transformation. The electron transfer from the hostnanotube to the reacting guest-molecules is essential for stabilising the anionic metal iodide 2 nanoclusters and for their further transformation to metal disulphide nanoribbons synthesised in the nanotubes in high yield.Keywords: Carbon Nanotube, Charge Transfer, Nanoparticle, Nanoreactor, Nanoribbon Single-walled carbon nanotubes (SWNT) are among the most effective and universal containers for molecules. Provided that the internal diameter of the host-nanotube is wider than the critical diameter of the guest-molecule, the insertion of molecules into SWNT is spontaneous and, in some cases, such as fullerenes and their derivatives, irreversible due to the ubiquitous van der Waals forces dominating the host guest interactions between the nanotube and molecules [1]. Fullerenes [2,3] or organic molecules [4][5][6][7][8][9][10] encapsulated in SWNT can then be triggered to react inside the nanotube to form unusual oligomers and polymers [11][12][13], graphene nanoribbons [14][15][16], nanotubes [8,17] or extraordinary molecular nanodiamonds [9]. These examples clearly demonstrate the use of SWNT as nanoscale chemical reactors, where the structure of the macromolecular product can be precisely controlled by spatial confinement of the reactions in the nanotube channel.In contrast to organic molecules,...

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Section: Equationmentioning

confidence: 99%

Carbon Nanotubes as Electrically Active Nanoreactors for Multi-Step Inorganic Synthesis: Sequential Transformations of Molecules to Nanoclusters and Nanoclusters to Nanoribbons

et al. 2016

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“…A comparative study explores the difference in structure obtained when using different filling techniques [56]. Using sublimation of the (C 59 N) 2 dimer, the CÀC interfullerene bond dissociates generating two C 59 N .…”

Section: Functionalized Fullerenesmentioning

confidence: 99%

Carbon Nanotubes as Containers

Chamberlain

Giménez-López

Khlobystov

2010

Carbon Nanotubes and Related Structures

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“…It is well-known that the C 59 N radical (C 59 N • ) is very active and can easily lose or gain an electron through regioselective reactions by binding to other atoms or molecules. 8,9 According to previous works, [9][10][11] this binding occurs via the nearest carbon atom (C′) of N in the structure of C 59 N, as it is very active and easily bound with other atoms such as C or H. In our C 59 N@SWNT samples, both monomer and dimers of C 59 N molecules are found inside SWNTs, 4,10 and therefore it is very likely the n-type behavior is due to the charge transfer from encapsulated C 59 N to SWNT by such C′-C bonding (there is an unpaired electron in C 59 N • ). This is presented in the left diagram of Figure 3, in which a radical-ion-pair is drawn, indicating the partial charge transfer to the SWNT.…”

Section: Measurementsmentioning

confidence: 99%

Photoswitching in Azafullerene Encapsulated Single-Walled Carbon Nanotube FET Devices

Kaneko

Kong

et al. 2009

J. Am. Chem. Soc.

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The photoinduced electrical transport properties of C(59)N@SWNTs are investigated by assembling them into FET devices. Our findings demonstrate that azafullerene molecules inside SWNTs make nanotube FET devices very sensitive to UV light exposure by the decrease of source-drain current upon light exposure. The photoswitching effect is found to be dependent on wavelengths of light and becomes negligible when the wavelength is increased to 480 nm. The photoinduced electron transfer is proposed to take place inside C(59)N@SWNTs due to the specific electronic structure of C(59)N, the heteromolecule bonding of which is sensitive to light.

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Azafullerenes Encapsulated within Single-Walled Carbon Nanotubes

Cited by 50 publications

References 19 publications

Carbon Nanotubes as Electrically Active Nanoreactors for Multi-Step Inorganic Synthesis: Sequential Transformations of Molecules to Nanoclusters and Nanoclusters to Nanoribbons

Carbon Nanotubes as Electrically Active Nanoreactors for Multi-Step Inorganic Synthesis: Sequential Transformations of Molecules to Nanoclusters and Nanoclusters to Nanoribbons

Carbon Nanotubes as Containers

Photoswitching in Azafullerene Encapsulated Single-Walled Carbon Nanotube FET Devices

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