Interaction Between C60 Fullerene and Alkali Metals Demonstrating Superconductivity

A discret summation method [1] has been used to calculate the van der Waals dispersion interactions between an alkali metal atom and individual C₆₀ fullerene molecules, as well as between an intercalated alkali metal atom and the face-centred-cubic lattice of solid fullerite. It is known [2, 3] that the conductivities observed in the doped C₆₀ films vary considerably for different alkali atoms. Our interest was to investigate any correlation between these conductivities and the long range potential field behaviour. In the present study, we have obtained interaction potential curves of the C₆₀ fullerene molecule including within its cage, as well the potential field topography within the overall C₆₀ fullerite solid unit cell. We have found that for all intercalated alkali metals, except Cs, there are voids within the unit-cell of fullerite where the dopant experiences attractive interactions. Whereas on the other hand, inside the fullerene cage only Li and Na experience attractive forces. Importantly, it has been shown that the localization of the crystallographic sites [4] of doped alkali metals in fullerite coincide with the potential energy minima of long range van der Waals forces.     

Effect of high-pressure high-temperature treatment on the structure of a hexagonal modification of fullerite C<Subscript>60</Subscript>

Powder X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, and molecular dynamics have been employed to investigate structural transformations in hexagonal and cubic modifications of fullerite C₆₀ after the action of high pressure (4 GPa) within the temperature range 20–1450°C. It has been found that fullerene molecules polymerize to afford polymer structures only in the case of face-centered cubic samples. Under the effect of high pressure and temperature, fullerite C₆₀ with a hexagonal close-packed structure is initially transformed into the cubic modification and, then, forms polymerized structures, which, during an increase in the treatment temperature, become less stable and ordered than the same polymerized structures obtained directly from cubic fullerite C₆₀. X-ray photoelectron spectroscopy measurements suggest deformation of the cages of fullerene molecules in the polymerized structures.     

Oxidation of C60 and C70 fullerites in air

The oxidation of C₆₀ and C₇₀ fullerites and C₆₀/C₇₀ mixture is accompanied by the decomposition of the carbon frameworks of the molecules at annealing temperatures of 250 and 445°C. Fourier-IR and HPLC studies show that the oxidation/decomposition of C₇₀ molecules is more active than that of C₆₀. The stages of fullerite interaction with oxygen while heating in air were determined.     

Chemical Bonding of Fullerene and Fluorinated Fullerene on Bare and Hydrogenated Diamond

We investigate the interface between a C₆₀ fullerite film, C₆₀F₃₆, and diamond (100) by using core‐level photoemission spectroscopy, cyclic voltammetry (CV), and high‐resolution electron energy loss spectroscopy (HREELS). We show that C₆₀ can be covalently bonded to reconstructed C(100)‐2×1 and that the bonded interface is sufficiently robust to exhibit characteristic C₆₀ redox peaks in solution. The bare diamond surface can be passivated against oxidation and hydrogenation by covalently bound C₆₀. However, C₆₀F₃₆ is not as stable as C₆₀ and desorbs below 300 °C (the latter species being stable up to 500 °C on the diamond surface). Neither C₆₀ fullerite nor C₆₀F₃₆ form reactive interfaces on the hydrogenated surface—they both desorb below 300 °C. The surface transfer doping process of hydrogenated diamond by C₆₀F₃₆ is the most evident one among all the adsorbate systems studied (with a coverage‐dependent band bending induced by C₆₀F₃₆)_.     

Thermodynamic properties of some polymeric forms of fullerite C<Subscript>60</Subscript> at temperatures ranging from 0 to 320 K

The temperature dependences of the heat capacityC ⁰ _p of fullerites C₆₀ were studied at temperatures ranging from 5 to 320 K in an adiabatic vacuum calorimeter with an accuracy of 0.4–0.2%. The fullerite C₆₀ samples were prepared by treating the starting fullerite C₆₀ under 8 GPa at 920 and 1270 K and “quenched” by a sharp decrease in pressure to −10⁵ Pa and in temperature to ∼300 K. Fullerite C₆₀(8 GPa, 920 K), a crystalline polymer with layered structure formed by polymerized fullerene C₆₀ molecules, was obtained at 920 K and 8 GPa. Fullerite C₆₀(8 GPa, 1270 K), a three-dimensional polymer with a graphite-like structure formed by fragments of decomposed C₆₀ molecules and containing many C(sp³)−C(sp³) bonds, was obtained at 1270 K and 8 GPa. Both polymers are metastable polymeric phases. The anomalous character of the temperature dependence of the heat capacity was revealed in the 49–66 K range for the polymer formed at 1270 K. The thermodynamic functions of the substances under study were calculated for the 0–320 K region along with entropies of their formation from graphite. The entropies of transformation of the starting fullerite C₆₀ into metastable phases and that of intertransformation of phases were estimated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 277–281, February, 2000.     

Investigation of phase interactions in C<Subscript>60</Subscript> fullerite films during gas phase metal deposition

Fullerite films covered with d-metal layers were obtained. The metal deposited over fullerite was shown to diffuse substantially into the films. The prepared heterophase film structures M/C₆₀ were studied by X-ray diffraction and vibrational spectroscopy. It is established that the interaction between metal and fullerite phases gives rise to chemical bonds M—C₆₀. It results in a partial polymerization of fullerite. Samples of metal-impregnated fullerite films exhibit semiconducting properties.     

Thermal properties of Fe-fullerene systems is reaction C60+Fe→Fe@C60 in solid fullerite possible?

Iron in the fullerite lattice binds fullerences in a sandwich type C₆₀FeC₆₀ complexes. At the concentration C₆₀Fe₂ it crystallizes in the monoclinic lattice. The structure is thermally unstable, with the energy release of 606 kJ·mol^?1 it returns to fee lattice. Two possible sites in the reconstructed fee lattice are discussed, Fe bond to C₆₀ and Fe inside the C₆₀ cage.     

Features of the oxidation of C<Subscript>60</Subscript> and C<Subscript>70</Subscript> fullerites as studied by IR spectroscopy

Features of the oxidation of C₆₀ and C₇₀ fullerites were studied by infrared spectroscopy. It was shown that for C₆₀ fullerite, the presence of toluene residue reduces the temperature at which oxidation starts. The form of the toluene (solvate or nonsolvate) is not important. A low-frequency shift in the valence C-O-C vibrations of C₇₀ fullerene due to local steric strains was discovered.     

Doping of fullerite with molecular oxygen at low temperature and pressure

Two methods are described for doping of fullerite C₆₀ with molecular oxygen at a pressure of ∼104 Pa and at temperature 20–30 °C. It was found by mass spectrometry using oxygen ¹⁸O as dopant that a portion of molecular oxygen absorbed by the pre-decontaminated fullerite (first method) is removed as CO and CO₂ at the heating temperature ≤200 °C. Doping during fullerite precipitation from the liquid phase (second method) makes it possible to prepare samples with the oxygen content ≥1.2 at.%. The fullerite doped with oxygen to this level is diamagnetic. The paramagnetic properties of an O₂ molecule disappear when O₂ is incorporated into the fullerene lattice. This is interpreted on the basis of quantum chemical calculations as a sequence of equilibrium formation of the adduct C₆₀O₂. Calculations showed that the subsequent chemical transformation of C₆₀O₂ resulting in the O-O bond cleavage is energetically favorable, enabling prerequisites for the formation of products of incomplete (CO) and deep (CO₂) oxidation of fullerene under mild conditions. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 662–671, April, 2006     

On the state of CH<Subscript>4</Subscript> molecule in the octahedral void of C<Subscript>60</Subscript> fullerite

Methane-intercalated fullerite (CH₄)_0.56C₆₀ was obtained by low-temperature precipitation from solution. Methane transition from the gas phase to the octahedral void of fullerite is accompanied by a bathochromic shift of normal vibrational frequencies (by 19 and 8 cm⁻¹ for ν₃ and ν₄, respectively). The methane ¹³C signal in the proton decoupling ¹³C NMR spectrum is observed as a singlet at δ−0.42. According to quantum chemical calculations using density functional theory, location of methane in the octahedral void of fullerite (C₆₀)₆ leads to a decrease in the total energy of fullerite by 4 kcal mol⁻¹.     

Conversion of isopropyl alcohol to acetone in fullerite cavities

Fullerite with cavities containing dichlorobenzene (DCB) and isopropyl alcohol (IPA) molecules was prepared by the addition of IPA to a solution of fullerene C₆₀ in DCB. On heating in vacuo fullerite evolves IPA, and the temperature increase to 200—350 °C results in the evolution of acetone. No products of DCB conversion were observed. Possible products of the interaction of 60 with two IPA molecules were calculated by the quantum chemical method. New data on the fullerite structure were obtained by transmission electron microscopy X-ray powder diffractometry, mass spectrometry, IR spectroscopy, and other methods. One of the possible mechanisms of the reaction IPA → acetone was considered.     

Features of electrochemical and thermal properties of CsHSO<Subscript>4</Subscript>-C<Subscript>60</Subscript> composite materials

New composite proton-conducting materials based on cesium hydrosulfate with fullerite C₆₀ were synthesized. The concentration dependence of the proton conductivity and thermal properties of synthesized materials with C₆₀ contents from 0 to 50 vol % was studied. It was found that these dependences are nonmonotonic with extrema at C₆₀ contents of ～2 and 30 vol %. The conductivity of the composite material with a C₆₀ content of ～2 vol % is almost twice higher than the conductivity of pure CsHSO₄ due to the formation of a new surface phase, which is confirmed by thermal analysis methods.     

Fullerite intercalated with argon at room temperature: Synthesis and physicochemical properties

Fullerite with the bulk formula Ar _x C₆₀, where 0.60 < x < 0.75, was synthesized by precipitation from a mixture of argon-saturated solutions. The fcc unit cell parameter in the sample was 1.422 nm; the orientational phase transition (OPT) temperature was 247 K. These values noticeably differ from the relevant parameters of undoped fullerite (1.416 nm and 260 K, respectively). Heating accompanied by argon evolution restores the fullerite C₆₀ structure.     

Could alkaline–earth-intercalated fullerites actually be semimetals?

Ab initio Hartree–Fock crystal-orbital calculations on three ideal fullerite C₆₀ crystals doped with strontium (C₆₀Sr_N, where N=2, 3, 6) are reported. C₆₀Sr₃ is calculated here to be a semiconductor; C₆₀Sr₂, a zero-gap semiconductor, and C₆₀Sr₆, a one-dimensional metal. The C₆₀Sr_N are found to be highly ionic as well: The total charge transfers are 3.444, 4.956, and 9.228 e for N=2, 3, and 6, respectively. The possible mechanisms of the observed superconductivity in C₆₀Sr₆ are discussed. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 69: 201–208, 1998     

Interaction in fullerene—ammonia system at 423—773 K

The interaction of C₆₀ fullerite and C₆₀—NH₄Cl mixture (8 wt. % of NH₄Cl, promoter of reaction) with ammonia was investigated at a starting NH₃ pressure of 0.6—0.7 MPa in the temperature range 423—773 K. Raising the temperature to 723 K is accompanied by hydrogenation and nitrogenation of the C₆₀ matrix. Treatment of fullerite with ammonia at 773 K is followed by the decomposition of the fullerene framework and formation of X-ray amorphous product. The physico-chemical properties of hydride-nitride phases formed during the interaction were investigated. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 217—219, February, 2006.     

Low-Cost Synthesis of Fullerene Derivatives

Refined mixed fullerenes were used as a reagent in known organic reactions instead of the pure fullerene C₆₀ with aim to find an alternative, low-cost method for the synthesis of fullerene derivatives potentially exhibiting photoconductive properties. The isolation of C₆₀ or C₇₀ in clean form without admixtures requires the use of large quantities of toluene or other nonpolar solvents, polluting the environment and multiplying the production cost. 1,3-Dipolar cycloaddition of azomethine ylide to fullerite was chosen because this reaction is one of the most widely used for fullerene functionalization, producing material possibly presenting photoinducing behavior. The data showed that the use of the cheaper mixed fullerenes instead of pure C₆₀ leads to the isolation of the same expected products with similar yields. The photoelectric properties of mixed fullerenes and their organic derivatives were also examined. A slightly semiconductive behavior was confirmed as well as a noticeable photoresponse.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.     

Fullerite with intercalated freon Ch2F2

Fullerite C₆₀ with intercalated CH₂F₂ (Freon-32) was prepared for the first time. The sample was studied by elemental analysis, X-ray powder diffraction, mass spectrometry, and IR spectroscopy. The composition of the sample was found to be (CH₂F₂)C₆₀. The sample had a face-centered cubic lattice with the lattice parameter (1.4284 nm) much larger than that of pure fullerite (1.416 nm). The gas released from the sample during heating in a vacuum to 450°C largely consisted of initial Freon (mass spectrometry data); no Freon destruction products were observed at this temperature. The C-F stretching vibration frequency (1058 cm^?1) was shifted in (CH₂F₂)C₆₀ by 30 cm^?1 toward lower wave numbers compared with the gas phase. The absorption bands at 1182 and 1428 cm^?1 (IR active modes (F _1u ) of high-symmetry (I _h ) C₆₀ molecules) did not change their positions in the intercalate.     

Pressure effect on heterogeneous trifluoromethylation of fullerenes and its application

The first systematic study of heterogeneous fullerene trifluoromethylation using an innovative gradient-temperature gas-solid reactor revealed a significant effect of CF₃I pressure on the conversion of C₆₀ and C₇₀ into trifluoromethylated products and on the range of fullerene(CF₃)_n compositions that were obtained. The design of the reactor allowed us to lower the residence times of fullerene(CF₃)_n species in the hot zone which resulted in the significant differences in relative isomeric distributions as compared to the earlier methods. For the first time, gram quantities of trifluoromethylated fullerenes were prepared using the new reactor, and the selective synthesis of a single-isomer C₆₀(CF₃)₂ was developed. The relative reactivity of C₇₀ as a CF₃ radical scavenger was found to be much lower than that of C₆₀, especially at an early radical addition stage, which led to the cost-efficient synthesis of C₆₀(CF₃)₂ from a fullerene extract.     

The structure of fullerene films and their metallocene doping

Hexagonal close-packed (HCP) C₆₀ and C₇₀ films have been prepared by the Langmuir method and examined by electron microscopy and electron-diffraction analysis. It has been shown that the vacuum deposition of a C₆₀+C₇₀ mixture results in the formation of a film with small sized grains and a distorted C₆₀-HCP structure. The simultaneous deposition of C₆₀ and ferrocene results in the formation of a film with a changed morphology and an electron-diffraction pattern that contains a variable amount of ferrocene depending on the experimental conditions. The electron-diffraction pattern corresponds to the presence of the known molecular complex C₆₀[(C₅H₅)₂Fe]₂. The analogous simultaneous deposition of fullerene C₆₀ and cobaltocene results in the formation of a C₆₀ film stable in air and water, which contains carbon and cobalt (from the data of X-ray fluorescence, electron microscopy and microdiffraction). It has a different morphology and different diffraction patterns than pure C₆₀ films and, depending on the cobaltocene content (relative to that of fullerene), appears to be a fullerite film doped with various amounts of cobaltocenium fullende, which is an ionic compound.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1379–1383, August, 1994.The work was financially supported by the Russian Foundation for Basic Research (Projects 93-03-4676 and 93-03-18368).     

Theoretical investigation on icosahedral C60(FeCp)12: A hybrid of C60 and ferrocene

A perfect hybrid complex C₆₀(FeCp)₁₂ is predicted using density functional theory method_. This fullerene derivative could be view as a C₆₀ cage of which each C₅ ring coordinates a (FeCp) ligand. Theoretical calculation reveals that it has a large lowest unoccupied molecular orbital–highest unoccupied molecular orbital gap (2.53 eV) and keeps the I_h symmetry of C₆₀. But the C? C bond length of its inner C₆₀ cage trends to be uniform, which is quite different from the bonding character of C₆₀ fullerene. Further investigation reveals that the chemical bonding, TDOS and the aromaticity of the (C₅FeCp) unit in C₆₀(FeCp)₁₂ are similar as those of ferrocene molecule, which indicates the similarity of their electronic properties. So, this compound could be viewed as the combination of ferrocene molecules. Thus, its unconventional formation process from 12 Fe(Cp)₂ is proposed and the reaction energy is calculated. As the C₆₀(FeCp)₁₂ compound has the geometry framework as C₆₀ and the electronic characters as ferrocene, it would inherit the outstanding properties from both two molecules and have wild potential applications in nanochemistry. We hope our study could give some references for the further investigation and experimental synthesis research of the C₆₀(FeCp)₁₂ compound. © 2015 Wiley Periodicals, Inc.