Search

We report the preparation of organometallic side-wall complexes of single-walled carbon nanotubes (SWNTs) under conditions, which allow the study of both mono- and bis-hexahapto SWNT coordination compounds [(η6-SWNT)Cr(CO)3, (η6-SWNT)Cr(η6-C6H6), (η6-SWNT)2Cr]. The results are interpreted in terms of exohedral and endohedral binding of chromium to the SWNT sidewalls and ligand competition reactions suggest that endohedral binding provides a very stable and kinetically inert mode of organometallic bonding. We demonstrate that the electrical conductivity of SWNT thin films are significantly enhanced by side-wall bonding to Group 6 transition metals (M = Cr, Mo, and W), which serve to reduce the inter-carbon nanotube junction electrical resistance by the formation of SWNT interconnects [(η6-SWNT)2M].

A high energy density supercapacitor device is reported that utilizes hybrid carbon electrodes and the ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4) as an electrolyte. The hybrid electrodes are prepared from reduced graphite oxide (rGO) and purified single-walled carbon nanotubes (SWCNTs). A simple casting technique gives the hybrid structure with optimum porosity and functionality that provides high energy and power densities. The combination of SWCNTs and rGO in a weight ratio of 1:1 is found to afford a specific capacitance of 222 F g−1 and an energy density of 94 Wh kg−1 at room temperature.

We report the preparation, crystallization, and solid state characterization of a new benzannulated phenalenyl radical; a distinctive feature of this molecular solid is the absence of any well defined conducting pathway(s). In the solid state, the radicals exist as π-dimer and the requisite C···C contacts between dimers are all larger than the sum of the van der Waals distances. The magnetic susceptibility measurement indicates that, in the solid state, the radical remains paramagnetic and the fraction of Curie spins is 0.55 per molecule. Pressed pellet conductivity measurements indicate a value of σRT = 0.5 × 10−6 S/cm. The conductivity value is comparable with those of similarly packed phenalenyl based neutral radicals. Copyright © 2012 John Wiley & Sons, Ltd.

We report the synthesis, crystallization, and solid-state characterization of the 3,7-ethoxy-substituted spirobiphenalenyl-boron neutral radical 22. The radical is distinguished by its low disproportionation energy and one-dimensional structure. We show that our strategy of substitution of OEt group at the active positions of the phenalenyl units changes the crystal packing from its previously known OMe analogue and the solid-state properties are dictated by the partial π-stack structure and the oxygen atoms at the 3,7-positions and can be best rationalized in terms of the resonating valence bond model. Magnetic susceptibility measurements show that in the solid state the radical remains paramagnetic but there is significant spin-spin interaction between the molecules. Band structure calculations reflect efficient overlap between the molecules along the π stack and show evidence of interactions between the spin-bearing oxygen atoms. The room temperature electrical conductivity (σ(RT)=2.0×10(-2) S cm(-1)) of 22 is higher than that observed in previously known one-dimensional phenalenyl radicals.

International audience; Graphene displays unprecedented electronic properties including room-temperature ballistic transport and quantum conductance, and because of its small spin-orbit interaction, graphene has the potential to function as the building block of future spintronic devices. Theoretical calculations indicate that a defective graphene sheet will be simultaneously semiconducting and magnetic; thus it would act as a room-temperature magnetic semiconductor. Recently, ferromagnetic ordering at room temperature has been observed by magnetometry measurements on bulk samples of reduced graphene oxide.

Treatment of carbon nanotubes by oxidizing acids is extensively used to dissolve metal residues from raw nanotube samples. The effect of acid treatment on the tubes themselves is twofold: it introduces uniform carboxylic sidegroups on the tube ends and defects, and it increases the overall charge concentration on the nanotube walls, thereby p-doping the material. Wide-range optical spectroscopy is an ideal tool to characterize both effects from one type of measurement: vibrational signatures indicate the presence of the sidegroups, the increase in far-infrared absorption signals the presence of free carriers, and the disappearance of interband transitions is the consequence of the depletion of Van Hove singularities when introducing holes. We have subjected carbon nanotube samples to two kinds of acid treatment: mild (in HNO(3) vapor at room temperature) and aggressive (high-temperature reflux). We found that on mild treatment, electronic doping occurs without defect oxidation to carboxylic groups, while the aggressive procedure leads to both doping and defect oxidation. Our spectroscopic data unambiguously prove that the changes in electrical conductivity on acid doping are intrinsic, and not just a result of improving the contact between nanotubes. Refereed/Peer-reviewed

We present optical spectra from the far infrared through the ultraviolet spectral region of freestanding transparent carbon nanotube films : single-, double- and multiwalled, and containing varying amounts of tubes of different chirality. By comparing the spectral features in the far infrared and the near infrared/visible, we can estimate the metallic/semiconducting content. We show by spectroscopic methods that doping the tubes increases both the conductivity and the transparency for visible light.We also discuss the influence of sample preparation and subsequent treatment on application possibilities.

We report the electropolymerization and characterization of polypyrrole films doped with poly(m-aminobenzene sulfonic acid (PABS) functionalized single-walled nanotubes (SWNT) (PPy/SWNT-PABS). The negatively charged water-soluble SWNT-PABS served as anionic dopant during the electropolymerization to synthesize PPy/SWNTPABS composite films. The synthetic, morphological and electrical properties of PPy/SWNT-PABS films and chloride doped polypyrrole (PPy/Cl) films were compared. Characterization was performed by cyclic voltammetry, atomic force microscopy (AFM), scanning electron microscopy (SEM) and Raman spectroscopy. SEM and AFM images revealed that the incorporation of SWNT-PABS significantly altered the morphology of the PPy. Cyclic voltammetry showed improved electrochemical properties of PPy/SWNT-PABS films as compared to PPy/Cl films. Raman Spectroscopy confirmed the presence of SWNT-PABS within composite films. Field effect transistor (FET) and electrical characterization studies show that the incorporation of the SWNT-PABS increased the electronic performance of PPy/SWNT-PABS films when compared to PPy/Cl films. Finally, we fabricated PPy/SWNT-PABS nanotubes which may lead to potential applications to sensors and other electronic devices.

9-Hydroxyphenalenone is a planar multicyclic beta-keto-enol that demonstrates C2V symmetry on the NMR timescale. Off-axis substitution breaks the molecular symmetry and results in tautomers. 1H and 13C NMR assignments were made for 9-hydroxyphenalenone and three methyl derivatives, and the solution-phase tautomers were determined.

Poly(m-aminobenzene sulfonic acid) (PABS), was covalently bonded to single-walled carbon nanotubes (SWNTs) to form a water-soluble nanotube–polymer compound (SWNT–PABS). The conductivity of the SWNT–PABS graft copolymer was about 5.6 × 10–3 S cm–1, which is much higher than that of neat PABS (5.4 × 10–7 S cm–1). The mid-IR spectrum confirmed the formation of an amide bond between the SWNTs and PABS. The 1H NMR spectrum of SWNT–PABS showed the absence of free PABS, while the UV/VIS/NIR spectrum of SWNT–PABS showed the presence of the interband transitions of the semiconducting SWNTs and an absorption at 17 750 cm–1 due to the PABS addend.

A new class of phenalenyl-based neutral radical molecular conductors has recently been reported; a distinctive feature of these molecular solids is the absence of the well-defined conducting pathway(s) that are characteristic of the organic charge- transfer salts. These radicals do not stack in the solid state, and the requisite carbon- carbon contacts are all larger than the sum of the van der Waals distances. Magnetic susceptibility measurements show that these compounds usually exist as isolated free radicals with one spin per molecule (at least over some temperature range), apparently supporting the idea that there is little interaction between the molecules in the solid state. Nevertheless, these radicals show the highest conductivity (RT 0.05 S/cm) of any neutral organic solid and the conduction mechanism is at present unresolved. In this article we report a structurally related radical with a resistivity five orders of magnitude higher than that of the previously reported radicals. We analyze the crystallographic and electronic structure of this solid in detail and point out some of the challenges that remain in relating structure, magnetism, and conductivity in this new class of organic solids. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 95: 853- 865, 2003

In this Perspective, we present an overview of recent fundamental studies on the nature of the interaction between individual metal atoms and metal clusters and the conjugated surfaces of graphene and carbon nanotube with a particular focus on the electronic structure and chemical bonding at the metal–graphene interface. We discuss the relevance of organometallic complexes of graphitic materials to the development of a fundamental understanding of these interactions and their application in atomtronics as atomic interconnects, high mobility organometallic transistor devices, high-frequency electronic devices, organometallic catalysis (hydrogen fuel generation by photocatalytic water splitting, fuel cells, hydrogenation), spintronics, memory devices, and the next generation energy devices. We touch on chemical vapor deposition (CVD) graphene grown on metals, the reactivity of its surface, and its use as a template for asymmetric graphene functionalization chemistry (ultrathin Janus discs). We highlight som...

The reactivity of the fullerenes is primarily a function of their strain, as measured by the pyramidalization angle or curvature of the conjugated carbon atoms. A consideration of the orientation of the π-orbitals shows that η2-complexation reactions lead to reaction products with the fullerenes that are very similar to those obtained from unstrained alkenes. Furthermore, a large amount of strain energy is released in this reaction, so it is clear just why this reaction is important in fullerene chemistry. On the other hand, it is shown that the π-orbitals of C60 are poorly oriented for overlap with an exohedral metal atom centered over the five- or six-membered rings, but well disposed for overlap with an endohedral metal atom centered under the five- or six-membered rings. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 139–143, 1998

Single-walled carbon nanotubes (SWCNTs) have unique electronic, mechanical, and structural characteristics; consequently, promising applications derived from these materials, such as chemical sensors or nanometer-scale electronic devices, can be expected. Structurally altered nanotubes with appropriate addends should facilitate their use by improving solubility, processability, and ease of dispersion, as well as by providing sites for chemical attachment to surfaces and polymer matrices. Avexing problem is ascertaining the detailed structures of nanotube derivatives after their preparation. The characterization of functionalized SWCNTs is difficult; all experimental attempts to determine the precise location and mode of addition of newly attached groups have failed. SWCNT adducts with possible three-membered rings (3MRs) that result from oxygen, methylene, and NH additions are simple but very important side-wall functionalized derivatives. Oxidation reactions are used widely to purify nanotubes, and the electrical properties of carbon nanotubes are extremely sensitive to oxygen exposure. Methylene and NH adducts are the prototypes of the recently synthesized covalently bonded dichlorocarbene and nitrene adducts. The available theoretical studies on the structures of nanotube oxide and dichlorocarbene adducts that involve either armchair or zigzag tube models, employed rather unsatisfactory methodology (see below). Owing to the large size of nanotubes, carefully chosen truncated models, appropriate for the problem being investigated, are required. One approach uses small nanotube fragments to simulate a full nanotube, but carries out computations at a relatively high level. The other approach uses the ONIOM technique, which treats part of the system at a high theoretical level but the rest of the system at a lower level. This strategy allows larger systems to be simulated at a practical computational cost. Thus, a recent ONIOM(B3LYP/6-31G*:AM1) study employed a C16 fragment (Figure 1a) for the high-level computation to

Chemistry will play an increasingly important role in the realization of graphene applications. The chemical formation of covalent carbon–carbon bonds involving the basal plane carbon atoms offers an alternative approach to the control of the electronic properties of graphene, and potentially allows the generation of insulating and semiconducting regions in graphene wafers. This review summarizes recent progress in the covalent modification of epitaxial graphene and the effect that chemistry has on the electronic and magnetic properties of the material.

Photoemission spectra of vacuum deposited layers of C 60 , before and after exposure to K vapor, show that the K donates its conduction electron into the band derived from the lowest unoccupied molecular orbital. A compound with composition of K 3 C 60 , corresponding to the maximum conductivity, has been prepared. In it the potassium atoms presumably occupy both the octahedral and the two tetrahedral interstitial sites of the face-centered-cubic (fcc) C 60 structure.

The curvature and topology required for fullerene formation strongly enhances the electronegativity of the carbon clusters and as a result c60 readily accepts electrons. Solid c60 undergoes doping with alkali metal vapors to produce intercalation compounds which are conductors.During the doping process the predominant phases present are: C60r and A&). The compounds are formed from c60 by occupancy of the interstitial sites of the fcc lattice.These phases constitute the first three-dimensional organic conductors and for A = K, Rb, the A3C6, compounds are superconductors.

BULK C60 (fullerite) is a solid composed of extremely hard pseudospherical molecules bonded by weak van der Waals interactions. We expect that pressurization will probe this diversity as the intermolecular distance is reduced. Here we present experimental measurements of the room-temperature pressure–volume equation of state of C60 fullerite to pressures of 20 GPa. The face-centred cubic phase remains stable under hydrostatic compression to this pressure, with an atmospheric-pressure isothermal bulk modulus of K0 = 18.1 ± 1.8 GPa and dK0/dP = 5.7 ± 0.6, characteristic of isotropic van der Waals intermolecular bonding. X-ray diffraction intensity changes are consistent with the compressibility of the C60 molecule being significantly lower than that of the bulk fullerite solid. Under non-hydrostatic compression, a transition to a crystallographic structure of lower symmetry is observed at 16±1 GPa.

Alkali metal fullerides (A x C 60 ) are a subject of considerable current interest because of the occurrence of superconductivity for A x C 60 at temperatures surpassed only by the high T c copper oxides. The preparation and characterization of A x C 60 (A = alkali metal, x = 2,3,4,6) by powder X-ray diffraction, NMR ( 13 C, 23 Na and 87 Rb), and d.c. magnetization are reported. The structures are described as intercalation compounds of the FCC structure of pristine c 60 or of hypothetical BCC or BCT structures. The structures and phase diagrams can be rationalized on the basis of ion size and electrostatic considerations. Only the A 3 C 60 compounds are metallic (and superconducting). The superconducting T c increases nearly linearly with unit cell size. EHT (Extended Huckel Theory) calculations and 13 C NMR relaxation measurements indicate higher densities of states for the higher T c compositions.

The formation energy, [Delta]H[sub f], of fullerite intercalation compounds A[sub n]C[sub 60] with A = Na, K, Rb, and Cs and n = 6 is measured using differential scanning calorimetry. The alkali metals, K, Rb, and Cs react with C[sub 60] powders readily and directly form the bcc A[sub 6]C[sub 60]. [Delta]H[sub f] values are found to be [minus]28, [minus]39, [minus]40, and [minus]47 kcal/mol per alkali metal for Na, K, Rb, and Cs, respectively. The activation energy of diffusion of the alkali metals Rb and Cs in the corresponding A[sub 6]C[sub 60] compound is evaluated to be approximately 30 kcal/mol. 25 refs., 4 figs., 1 tab.

INTERCALATING solid C60 with dopant atoms yields materials with a remarkable range of properties1. Alkali metal atoms, for example, readily form charge-transfer compounds2,3, AxC60 (where A is an alkali metal), which can be metallic, superconducting or insulating depending on the dopant concentration4–9. In all cases, the superconducting phase has a face-centred cubic (f.c.c.) structure and stoichiometry A3C60, which suggests a common mechanism for superconductivity dependent, at least in part, on the external coordination number of the C60 molecules. More recently, it has been shown10 that the alkaline earth metal calcium can also be intercalated with fulleride to form a superconducting phase, again with a f.c.c.-derived structure, near a Ca:C60 ratio of 5:1. Here we report the intercalation of fulleride with barium, in which a pure body-centred cubic phase with a lattice constant of 11.171 A is realized near a stoichiometry of Ba6C60. This phase is also superconducting (with a transition temperature of 7 K), suggesting that the mechanism of superconductivity is related to an intrinsic property of the C60 molecules, rather than the external coordination number.

Within the wr-orbital axis vector theory, the total rehybridization required for closure of the fullerenes is approximately conserved. This result allows the development of a structure-based index of strain in the fullerenes, and it is estimated that about 80 percent of the heat of formation of the carbon atoms in C60 may be attributed to a combination of v strain and steric inhibition of resonance. Application of this analysis to the geometries of structurally characterized organometallic derivatives of C60 and C70 shows that the reactivity exhibited by the fullerenes may be attributed to the relief of a combination of local and global strain energy. C60 is of ambiguous aromatic character with anomalous magnetic properties but with the reactivity of a continuous aromatic molecule, moderated only by the tremendous strain inherent in the spheroidal structure.