Neutron bombardment of C60 and C70 fullerenes: A spectroscopic and calorimetric study

C₆₀ and C₇₀ fullerenes were neutron-bombarded to an integral dose of 3.28×10¹⁶ n cm^?2. After the neutron treatment the trichloromethane soluble fraction was determined spectrophotometrically and C₆₀ insoluble fraction was found at 3.8% while the insoluble fraction of C₇₀ 17.9%. The formation of the CHCl₃ insoluble fraction is due to polymerization and incipient amorphization of the neutron-bombarded fullerenes where C₇₀ appears more sensitive to radiation damage than C₆₀. Raman spectroscopy was used for the characterization of the irradiated fullerenes as well as electron spin resonance (ESR) and electronic absorption spectroscopy on solid samples. Differential scanning calorimetry (DSC) to 630°C was employed for the determination of the Wigner energy of the neutron-damaged fullerenes. The results are consistent with a higher level of radiation damage reached by C₇₀ in comparison to C₆₀ at the same neutron dose.     

Raman Spectra of Chlorinated C60 and C70 Fullerenes

Abstract

Raman spectra of chlorinated C₆₀ and C₇₀ fullerenes prepared by photochlorination have been reported and discussed. The Raman lines suggest structural analogies with already fully characterized brominated fullerenes. Intense laser light irradiation cause a decomposition of fullerene chloro-derivatives leading to the formation of C₆₀ polymer.     

The Dark Reaction of C60 and of C70 with Molecular Oxygen at Atmospheric Pressure and Temperatures between 300 K and 800 K

Abstract

The solid fullerenes C₆₀ and C₇₀ react in deliberate and adventitious situations with molecular oxygen in a wide range of temperatures. Using thin films and polycrystalline bulk samples with well-defined structures and chemical histories we investigated the complex process from molecular intercalation over atomic adduct formation to deep oxidation and polymerisation which together describe the oxidation reaction. A combination of photoemission (UPS, XPS) photoabsorption (XAS), FT-IR, temperature-programmed and isothermal gravimetric measurements and DSC allowed to identify the existence and gradual interconversion of the three types of solid products besides the gas phase products CO and CO₂. Both fullerenes react along the same reaction path. The difference of the molecular structures results in different activation barriers in the initial step of intercalation and in the final step of cage-opening. The overall reactivity of both fullerenes is quite similar at temperatures above the gasification onset of 570 K. The formation of the various adduct compounds was found to exert a detectable influence upon the overall molecular shape of the fullerenes and a small effect on the electronic structure was observed. The only moderate differences in electronic and geometric structures of pristine and initially oxidised fullerenes precludes a pronounced molecule-by-molecule reaction control and allows the topochemistry of the intercalation to control the shape of the reaction interface. This control is less effective for C₇₀ than for the C₆₀ fullerene.     

Extraction equilibria in a fullerene-containing C<Subscript>60</Subscript>-C<Subscript>70</Subscript>-<Emphasis Type="Italic">o</Emphasis>-Xylene-<Emphasis Type="Italic">i</Emphasis>-butylamine-water system

Extraction equilibria of the liquid(I)-liquid(II) type have been studied for the first time in a system containing light fullerenes C₆₀ and C₇₀. The experiments were performed with a five-component mixture of fullerene C₆₀, fullerene C₇₀, o-xylene, ibutylamine, and water at 25°C. Isothermal diagrams describing the distribution of fullerene components between separating liquid phases have been obtained. The distribution coefficients of fullerenes (C₆₀ and C₇₀ concentrations in the xylene phase relative to those in the amine phase) are found to be almost constant and approximately equal to ～16.1 for both C₆₀ and C₇₀.     

Synthesis of C60-NBN and C70-NBN(N=L, 2) by DC arc Burning Method

Abstract

Macroscopic quantities of boron-doped fullerenes, such as C_60-nB_n and C_70-nB_n(n = 1, 2), were successfully synthesized by DC arc burning method, extracted by CS₂, and characterized by field desorption mass spectra. Among them C₅₈B₂ and C₆₈B₂ were extracted for the first time. The boron-doped fullerenes were found to be less stable than their pristine fullerene analogs. When the electric current becomes too high, no boron doped fullerene, but more higher fullerenes, were formed.     

Determination of C60 and/or C70 Concentrations

Abstract

Two methods of quantitative analyses of the fullerenes C₆₀ and C₇₀ are described. Quantitative Infrared Spectroscopy permits the determination of the concentrations of pure and mixed compositions of C₆₀ and C₇₀ in carbondisulfide solutions. Alternatively, the ratio of C₆₀/C₇₀ is analyzed by evaluating the lattice parameters of a solid solution of the fullerene species and cyclohexane according to Vegard's Law. Both methods show high accuracy and are suited for calibration of mass spectrometric analyses of fullerene samples.     

An Invariant of Carbon Arc Synthesis of Fullerenes

Abstract

The yields of fullerenes C₆₀ and C₇₀ were determined in a wide range of controlled parameters. The total yield of fullerenes varied from 3 to 24%. The molar relative contents C₆₀/C₇₀ appeared to be constant for all samples of toluene extracts of the soot and equal to 5.06 ± 0.1. The accuracy of this constancy (± 2%) was determined by application of a special mathematical processing to the spectra of toluene extracts.     

QUINUCLIDINE DERIVATIVES IN CYCLOADDITION REACTIONS WITH FULLERENES [60]- AND [70]-

Diels-Alder reactions of quinuclidines with fullerenes C₆₀ and C₇₀ and mono- and bisadducts from the fullerenes C₆₀ and C₇₀ are reported.     

Penultimate Intermediates to C60 and C70

Abstract

Penultimate intermediates leading to C₆₀ and C₇₀ fullerenes contain one or two pairs of pentalene units and 32 to 55 kcal/mol less stable than the final products. Energy barriers of pyracylene rearrangements from these intermediates to the final products are computed to be 118 to 125 kcal/mol in height by MOPAC/AM1, which are comparable to those of preceding steps in the Stone-Wales rearrangement cascade.     

HPLC Diode‐Array Analysis of C60 and C70 Polymeric Fullerene Oxides (Fullerene Polymeric Ozonides)

Abstract

It is shown by HPLC diode‐array analysis that the C₆₀ and C₇₀ polymeric fullerene oxides ([C₆₀]‐PFOs and [C₇₀]‐PFOs) which are polymeric ozonides, are composed by nine different components. The ozonide derivatives of C₆₀ and C₇₀ have been proved to be practically analogous in chemical structure and composition. The most important component of both [C₆₀]‐PFOs and [C₇₀]‐PFOs accounts for about 3/4 of each sample. The overozonation of [C₆₀]‐PFOs in methanol has been studied and shown to not produce any significant changes.     

Nonlinear Stern-Volmer Fluorescence Quenching of Pyrene by C60/70

Abstract

The Stern-Volmer plot of fluorescence quenching of pyrene by C₆₀ (or C₇₀) is upward, and non linearly proportional to the fullerene concentration. Electronic absorption measurements show that pyrene and C₆₀ do not form static complexes under the experimental condition. a novel “inner filter effect” model is proposed to rationalize the observed non linear upward Stern Volmer behavior. At a given C₆₀ concentration, increasing either solvent polarity or temperature (T > 280 K) causes diminishment in the I₀/I ratio. the data strongly suggest that even at concentrations far below saturation, fullerenes form aggregates in organic solvents.     

Thermodynamic functions for the formation of isomeric CF3 adducts of C70 and C84

Gas-phase formation enthalpies and Gibbs energies of formation (Δ_fH°_m; Δ_fG°_m) of trifluoromethylderivatives of fullerenes C₇₀ and C₈₄ are calculated at the DFT (density functional theory) level of theory. The approach employs homodesmic (HD) transtrifluoromethylation reactions and experimental thermochemical data on C₆₀, C₇₀, C₈₄ and S₆-C₆₀(CF₃)₁₂.     

A STUDY ON THE THERMAL STABILITY TO 1000°C OF VARIOUS CARBON ALLOTROPES AND CARBONACEOUS MATTER BOTH UNDER NITROGEN AND IN AIR

ABSTRACT

The thermal behavior of graphite, C₆₀ fullerene, fullerene black (carbon soot containing fullerenes), extracted fullerene black and diamond has been analyzed to 1000°C by TGA–DTA (thermogravimetric analysis and differential thermal analysis) under a nitrogen flow at a heating rate of 20°C/min. Very small weight losses have been recorded in the case of graphite and diamond. Furthermore no diamond graphitization has been observed. The sublimation of pure C₆₀ and the fullerene fraction of fullerene black (both pristine and extracted) has been observed and discussed.

The combustion reaction in air flow of graphite, C₆₀ and C₇₀ fullerenes, fullerene black (both unextracted and extracted), carbon nanotubes and diamond has been studied by TGA–DTA at a heating rate of 20°C/min. C₇₀ fullerene and fullerene black have been found to be the most reactive carbon materials with O₂. The role played by C₇₀ in the degradation of fullerites has been discussed. Among the carbon materials examined, the best resistance to O₂ attack has been shown by diamond and carbon nanotubes. The behavior of graphite is intermediate between diamond and fullerene blacks. The behavior of C₆₀ fullerene appears closer to that of graphite although it appears to be more reactive with O₂. Samples of graphite and carbon blacks N375 and N234 have been studied by TGA–DTA in air flow before and after a radiation treatment with neutrons or γ radiation. The effect of the radiation damage in the combustion reaction of these carbon materials has been discussed.     

C60H18, C60H36 and C70H36 Fullerene Hydrides: Study by Methods of IR,NMR, XPS,EELS and Magnetochemistry

Abstract

Fullerene hydrides of C₆₀H₁₈, C₆₀H₃₆ and C₇₀H₃₆ are studied by using IR, ¹H and ¹³C NMR, X-ray photoelectron and electron energy loss spectroscopies, and magnetochemistry. The comparison of IR and solid state ¹H and ¹³C NMR data for C₆₀H₃₆ with the theoretical ones allows the suggestion that fullerene hydride has a T symmetric structure and contains 4 isolated benzenoid rings located at tetrahedral positions on the surface of a closed skeleton of the molecule. The EELS revealed that the transition from fullerene to the hydride is accompanied by the decrease of the density of valence electrons. Magnetization measurements showed C₆₀H₃₆ to be a ferromagnet. The hydrogenated fullerenes were prepared by transfer hydrogenation procedures involving 9,10-dihydroanthracene. The compositions of the hydrides are determined by field desorption mass-spectral analysis.     

Effect of Molecular Rotation on Vapor Phase Nucleation: Fullerenes C60 and C70

Abstract

The effect of rotational free energy of fullerenes C₆₀ and C₇₀ on homogeneous nucleation of crystals from vapor phase have been studied. Classical nucleation parameters have been estimated for the case of nucleation and crystal growth of C₆₀ and C₇₀ by Physical Vapor Transport (PVT) method under different supercooling in the range of 20–150 K, keeping the source temperatures constant. The result shows that the growth of large size single crystals is more feasible in the lower supercooling range. The effect of change in interfacial tension on the critical free energy of formation of the nuclei is also studied.     

Prospects of the use of fullerenes for the orientation of liquid-crystalline compositions

The dynamic characteristics of liquid crystal (LC) structures containing fullerenes C₆₀ and C₇₀ were studied, and the effect of fullerenes on the reorientation capacity of liquid crystal molecules was assessed. It is established that fullerenes C₆₀ and C₇₀ influence the operation time of polymer-dispersed LC cells containing photosensitive 2-cyclooctylamine-5-nitropyridine molecules. A possible mechanism of reorientation in the system is considered, and it is shown that fullerenes can provide for effective switching of the electrooptical response in such LC cells. Fullerenes have good prospects for use in orienting coatings of various types employed in the LC technology.     

About the iron carbonyl complex with C60 and C70 fullerene: [Fe(CO)4(η2C60)] and [Fe(CO)4(η2C70)]

The iron carbonyl complexes with C₆₀ and C₇₀ fullerenes were synthesized in high yield by photochemical irradiation of solutions of C₆₀ and C₇₀ in presence of Fe(CO)₅. The resulting complexes were studied by FT-IR, Raman and electronic absorption spectroscopy. All the data are consistent with the structures [Fe(CO)₄(η²C₆₀)] and [Fe(CO)₄(η²C₇₀)]. The thermal stability and decomposition reaction of the two complexes were studied by TGA-FTIR and Differential Scanning Calorimetry (DSC). Both complexes decompose at moderate temperatures releasing CO and Fe(CO)₅ in the vapor phase leaving a residue of metallic iron and free C₆₀ or C₇₀ fullerenes that can be recovered by solvent extraction of the decomposition residue.     

Kinetics of Fullerene Formation in a Contact Arc Generator

Abstract

A kinetic model of the fullerene growth process in a contact arc generator is developed. On the basis of the kinetic model, the yield of the magic fullerenes C₆₀ and C₇₀ is calculated. The fullerene yield is determined by the temperature gradient in the fullerene formation zone, the carbon vapor concentration and the helium jet velocity in the interelectrode space. We found that the upper boundary value of the magic fullerene yield was about 20%.     

Fullerene Research in Poland

Abstract

Main results of the investigations of fullerene and its derivatives are briefly reviewed. Such topics as plasma spectroscopy, fullerenes and nanotubes formation, C₆₀ carbyne knots, fullerene reduction and doping, charge transfer states and electroabsorption of C₆₀, electrical conductivity, superconductivity, ESR properties, fullerene clathrates, C₆₀/C₇₀ complexes with organic donors, fullerene adducts, hydrogenated fullerenes, metallofullerenes and carbon nanotubes are discussed.     

Thin fullerene-containing films synthesized by ion beam sputtering of fullerene mixtures with doping additives in vacuum

A new approach to the synthesis of films containing fullerenes and doping elements is described. It is suggested that a cluster mechanism of the target sputtering by accelerated ions makes possible the deposition of fullerenes on a substrate with a certain probability for dopant atoms being introduced into the cavities of fullerene molecules and a higher probability of their occurrence between fullerene molecules. The proposed method has been experimentally implemented by using an Ar⁺ ion beam to sputter C₆₀/C₇₀ fullerene mixtures (synthesized in a plasmachemical reactor at a pressure of 10⁵ Pa) pressed into disk targets with a doping element (Fe, Na, B, Gd, or Se). The ion beam sputtering of dopant-containing fullerene mixtures in a vacuum of ～10^?2 Pa allowed micron-thick films containing C₆₀ and C₇₀ fullerenes and the corresponding dopant element (Fe, Na, B, Gd, or Se) to be grown on quartz substrates.