Synthesis of Radiolabeled Fullerenes C60 and C70

Abstract

The synthesis of radiolabeled C₆₀/C₇₀ for potential biochemical tracer studies was carried out. Vaporization under plasma are conditions (~3000C) of graphite rods impregnated with the ¹⁴C labeled steroid progesterone generates the expected C₆₀/C₇₀ mixture. Isolation and characterization of the ¹⁴C-C₆₀ is reported. Interestingly, the C₇₀ had more radioactivity than the C₆₀.     

Solubility of Fullerenes C60 and C70 in Seven Normal Alcohols and Their Deduced Solubility in Water

Abstract

The solubilities of C₆₀ and C₇₀ at 25°C in seven normal alcohols obey the relationship InY = a + bX + cX², where Y is solubility and X is the Hildebrand solubility parameter of the solvent. Extrapolation to the solubility parameter of water yields solubilities in water of 1.3′10^?11 (C₆₀) and 1.3′10^?10(C₇₀) ng/ml with an uncertainty of one order of magnitude.     

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.     

Quantitative Determination of C60 and C70 in Soot Extracts by High Performance Liquid Chromatography and Mass Spectrometric Characterization

Abstract

A quantitative HPLC method was applied to determine the amounts of C₆₀ and C₇₀ present in extracts of soot produced in the electric arc reactor and in flames. The combustion method was found to yield a higher C₇₀/C₆₀ ratio (0.67) compared with the evaporation experiment where the C₇₀/C₆₀ ratio amounts to 0.27.     

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.     

ESR Studies on C60.OX and C60.HMTTEF

Abstract

The electron spin resonance (esr) of C₆₀.O_x and C₆₀.HMTTEF (hexamethylentetratellurafulvalene) has been investigated at 9.36 GHz as a function of temperature. T (298 T 4 K). C₆₀.O_x shows an esr absorption of equal ‘g’ value to that of C₆₀ exposed to O₂ and light but is more intense. The C₆₀ in its pure form is in a singlet state. The impurity sites introduced by O₂ produce the esr absorption. The Curie - Weiss plots of inverse esr absorption intensity versus temperature indicate an antiferromagnetic TH = 50 for air exposed C₆₀ and 90K for C₆₀O_x. From the esr intensity at room temperature, the calculated number of free spins (S = 1/2) is =1/3 per mole of C_60-O_x. In case of C₆₀.HMTTEF, there is a very weak esr absorption at room temperature suggesting that the room temperature form is diamagnetic with very small charge transfer between C₆₀ and HMTTEF. This conclusion is consistent with the structure and magnetic susceptibility of this cocrystal. As the temperature is lowered, the equilibrium: AD <=> A?^? + D?⁺ is displaced towards the formation of free radical species, A?^? and D?⁺.     

New Developments on the Photochlorination of C60 and C70 Fullerene and Preparation of Fullerene Derivatives: Polyfluorofullerenes and Polyfullerols.

Abstract

Improved methods for photochlorination of C₆₀ and C₇₀ are described. The photoproducts fit respectively the average formulae C₆₀ Cl₄₀ and C₇₀ Cl₄₇. It is also shown that these photoproducts can be easily fluorinated by means of KF to give fluorofullerenes.

Polyhydroxyfullerene (fullerol) can be easily produced by the action of a methanolic solution of alkali over C₆₀ Cl₄₀.     

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.     

Spontaneous Decay of Highly-Charged Fullerene Ions C60Z+ and C58z+

Abstract

Using isotope-resolved, two sector field mass spectrometric techniques we have identified and investigated quantitatively the energetics and kinetics (in particular the kinetic energy release, KER) of the spontaneous decay reactions C_60–2m ^z+ → C_60-2m-p(z-1)+ ₊ C_p ⁺ with m = 0 or 1, z ranging from 3 to 6 and p = 2 and 4. The obtained KER results are not compatible with the properties expected for a single-step fissioning reaction as described by the liquid drop model. Therefore the present data had to be interpreted by a different fragmentation mechanism. This novel reaction sequence, termed auto charge transfer (ACT) reaction, is initiated by the statistically driven neutral C₂ (or C₄₎ evaporation followed by an electron transfer process from the receding C₂ (or C₄) fragment to the remaining highly-charged fullerene ion thereby leading finally to the two charged reaction products observed in the exit channel of the decay reaction. Moreover, in the case that a C₂ ⁺ loss from C₆₀z+ is occurring in the first field-free region we have been able to demonstrate that it is possible to observe in the second field-free region a subsequent C₂ evaporation from the C₅₈(z-1)⁺ fragment ion.     

Preparation of Two Novel C60 and C70 Fullerene Pyrrolidine Derivatives

Abstract

C₆₀ reacted with paraformaldehyde and DL-valine in dry toluene under nitrogen to give a monoadduct. Under the similar conditions,C₇₀ gave a bisadduct. Both products were characterized by FT-IR,UV-Vis,EI-MS and NMR.The studies of the cyclic voltammetry showed that the abilities of donating electron of the products were increased compared to C₆₀ and C₇₀ respectively.     

13C and Alkali NMR Studies of Electronic and Structural Properties of Alkali Fullerides

Abstract

Extensive NMR experiments have been performed both on the ¹³C and the alkali NMR in A_nC₆₀. In the superconducting A₃C₆₀. evidences for uniaxial molecular rotations of the C₆₀ and for a low T structural anomaly will be given. The linear chain structure of A₁C₆₀ is revealed by Magic Angle Spinning NMR, while its magnetic properties are studied by ¹³C and ⁸⁷Rb wideband NMR.     

C60 and C70 pressure-and-temperature transformations into fullerene-related forms

A two-stage pressure-and-temperature treatment of the C₆₀ and C₇₀ fullerites was carried out. C₆₀ and C₇₀ molecules collapsed at the first-stage hot-isostatic-pressing (HIP; 220 MPa, argon) and transformed into some fullerene-related form in the 900–1750°C temperature range. These materials were used at the second stage of the high-pressure-high-temperature (HPHT; 7.7 GPa/1400°C) treatment to produce the bulk samples that had: a specific weight of about 2.0 g/cm³, 40/110 GPa Young modulus, 6.0/12.5 GPa, and elastic recovery above 81%. Transformations under the treatments were investigated with the X-ray and transmission electron microscopy techniques. The mechanism of the pressure-and-temperature transformations is discussed.     

On Some Complexes of Allyl Derivatives of C60 Fullerene: Simulation of Molecular and Electron Structure by DFT

Abstract

The problem of existence of η³–π‐complexes of transition metal atoms with the allyl type derivatives C₆₀X₃ of C₆₀ fullerene is discussed. It is shown that complexes C₆₀X₃Co(CO)₃ (X = H, F, Cl, Br), C₆₀H₃NiC₅H₅, C₆₀H₃Fe(CO)C₅H₅, where three atoms X are bound to the C atoms of fullerene in the α‐positions relative to the same five‐membered ring in the C₆₀ fullerene, must be sufficiently stable. In these complexes the metal atoms are η³–π‐bound to the fullerene cage. In contrast to this, the metal atoms with the same allyl type C₆₀H₃ derivative of C₆₀ fullerene in the C₆₀H₃Li and C₆₀H₃FeC₅H₅ complexes are η⁵–π‐coordinated to the carbon cage. Calculations were carried out by the DFT with the exchange‐correlation potential by Perdew–Burke–Ernzerhow.     

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.     

Direct and Catalytic Hydrogenation of Buckminsterfullerene C60

Abstract

C₆₀H₁₈ was obtained by direct hydrogenation of C₆₀ at 400 C and 80 atm C₆₀ was hydrogenated to C₆₀H₃₆ as a main product in the presence of Pd/C catalyst at 180C and 30–70 atm. C₆₀H₃₆ is unstable in dichloromethane and some other organic solvents.     

Effects of Hexasulfobutylated C60 on the Thalamic Neurons in Neonatal Rat in vitro

Abstract

The effects of hexasulfobutylated C₆₀ (FC₄S) on membrane potentials and currents were studied by tight-seal, whole-cell recording in thin slices of the neonatal rat thalamus. Silent neuron with resting membrane potentials of around -62.4 ± 0.7 mV was found in whole-cell current clamp recordings. Hexasulfobutylated C₆₀ depolarized the neuron by a concentration dependent manner. It also (1) prolonged the decay time constant of action potential and (2) decreased the threshold of the directly elicited action potentials of the neuron. Hexasulfobutylated C₆₀ did not alter the input resistance of the excitable membrane. In whole-cell voltage clamp studies, depolarizing command pulses from a holding potential of about -70 mV evoked a fast inward current followed by an outward current in the thalamic neurons. Hexasulfobutylated C₆₀ (30 - 100 μM) increased the total inward sodium current of the neuron, while hexasulfobutylated C₆₀ did not alter the outward potassium currents in all voltage steps tested. It was concluded that hexasulfobutylated C₆₀ (1) decreased the threshold of the action potential and (2) prolonged the decay time constant of the directly elicited action potential of the neonatal rat thalamic neurons. The effect may be closely associated with the Na⁺ current in thalamic neurons.     

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.     

Sorption studies of helium and neon by crystals of C60 and C70

We present sorption measurements for³He and⁴He in the temperature range of 1.5 K to 4.1 K, and for²⁰Ne in the temperature range of 22 K to 27 K by crystals of C₆₀, C₇₀ and crystals of the mixture of these two molecules, 80% C₆₀, 20% C₇₀ We analyze these data by taking into account the non-ideality of the gas in equilibrium with the adsorbate. We calculate chemical potentials and isosteric heats. We find that there is no obvious evidence of intercalation of helium in these crystals at low temperatures. At higher temperatures there are some anomalies in the helium isotherms, and indication of excess sorption. The isosteric heat shows a minimum in this region which can be interpreted as penetration of the helium into a region of repulsive potential. We also find that levels of sorption, at the same chemical potential difference from saturation, are higher for⁴He than for³He. They are also higher for⁴He on C₇₀ than for the other crystals. For neon our work is concentrated around the triple point. We find that the isotherms indicate the formation of liquid or solid films. Below the triple point, and above a few atomic layers, the neon film does not grow uniformly.     

On the Action of Ultraviolet Light on C70 Fullerene

Abstract

C₇₀ was photopolymerized in solution of CCl₄ under nitrogen flow by an high pressure mercury lamp. The resulting photoproduct was still soluble in common solvents and has been studied by electronic and FT-IR spectroscopy. FT-IR spectroscopy reveals a very peculiar band pattern never reported to date for C₇₀ photoproduct. Since this band pattern is very similar to that of C₆₀ photopolymer, it suggests that C₇₀ photoproduct should have a chemical structure very close to that assigned to C₆₀ photopolymer and piezopolymer.

The role played by CCl₄ in C₇₀ photopolymerization seems to be comparable to that already reported for C₆₀, i.e. it acts as a polymerization promoter.     

Pressure dependence of superconductivity in Ba4C60

In Ba_xC₆₀ superconductivity (sc) at T_c=(6.8±0.2) K is associated with the x=4 phase. Here we present pressure studies of T_c of a Ba_xC₆₀ sample (dT_c/dp= –1.9 K/GPa) which exhibits a large volume fraction of the x=4 phase. In the alkali-fullerides K₆₀C₆₀ and Rb₃C₆₀ T_c is governed by the electronic density of states N(E_F) (T_c exp{–1/N(E_F)V}). The dependence of N(E_F) on volume can be approximated by N(E_F)=N₀ d _eff ³, where d_eff is the surface to surface distance of neighboured C₆₀-molecules. This relationship is corroborated by (T_C,d)-data of various compounds of the form A_3–xB_xC₆₀ (A: K, Rb; B: K, Rb, Cs; x2). Strong deviation from this behavior is found for the alkaline-fulleride superconductor Ba₄C₆₀. This deviation is attributed to the hybridization of alkaline-metal s-, d-states and C₆₀ -states.