Pressure-induced dimerization kinetics of fullerene C60

Dimerization kinetics was studied for fullerene C₆₀ by IR spectroscopy at a pressure of 1.5 GPa in the temperature range 373–473 K. The kinetic curves for the formation of a dimer (C₆₀)₂ were obtained using its analytical IR band at 796 cm^?1. Under the assumption that pressure-induced C₆₀ dimerization is a second-order irreversible reaction, the reaction rate constants were determined at different temperatures. The corresponding activation energy and preexponential factor were found to be 134±6 kJ/mol and (1.74± 0.24)×10¹⁴ s^?1, respectively. The specific features of the solid-phase C₆₀ dimerization in simple cubic and face-centered cubic fullerite phases are discussed.     

Optical limiting behavior of new fullerene derivatives

The optical limiting behavior of C₆₀Ph₅Cl, C₆₀Cl₆, and C₇₀Cl₁₀ in toluene solution has been measured at 532 nm with nanosecond pulses. The limiting threshold for C₆₀Ph₅Cl, C₆₀Cl₆, and C₇₀Cl₁₀ were 4, 8, and 8 J/cm², respectively. The limiting action was strongly influenced by the number of conjugated double bonds and the nature of the ligand. Both lower limiting thresholds and throughputs make these new fullerene derivative compounds good promising candidates for optical limiting materials in the toluene solution.     

Synthesis and photophysical properties of polyamides containing in-chain porphyrin and [60]fullerene

Conjugated polyamides containing porphyrin and [60]fullerene (C₆₀) in the main chain were prepared by a direct polycondensation of the 3′H,3″H-dicyclopropa[1, 9:16, 17] [5, 6]fullerene-C₆₀-I _h -3′,3″-dicarboxylic acid and 5,15-bis(4-aminophenyl)-10,20-bis(3,5-dialkoxyphenyl)porphyrin in the presence of triphenyl phosphite and pyridine. Gel permeation chromatography (GPC) analysis of the polyamides showed the weight-average molecular weight was about 23,626–23,736, and the temperature at 5% weight loss determined by thermogravimetric analysis (TGA) was above 216 °C. The transmission electron microscopy (TEM) images displayed the regular one-dimensional linear arrays of the polyamides with lengths exceeded 200 nm. The photoinduced electron transfer from porphyrin to C₆₀ in the polyamides was observed in nanosecond laser-flash photolysis experiments at ambient temperature, which produced a charge-separated state (porphyrin radical cation–C₆₀ radical anion pair) with a lifetime as long as 40 μs. The calculated ratio of k _CS/k _CR was found to be 2.1 × 10⁴. They could have potential applications for photoelectronic devices, organic solar cells and so on.     

The oxidation of fullerene [C70] with various oxidants by ultrasonication

The reaction of C₇₀ by ultrasonication with various oxidants such as 3-chloroperoxy benzoic acid (Fluka 99%), 4-methyl morpholine N-oxide (Aldrich 97%), chromium (VI) oxide (Aldrich 99.9%), and oxone^® monopersulfate compound, at room temperature causes the oxidation of fullerene [C₇₀(O)_n] (n=1–2 or n=1). The FAB-MS, UV–visible, FT-IR spectra, and HPLC analysis confirmed that products of fullerene oxidation are [C₇₀(O)_n] (n=1–2 or n=1).     

Ab initio calculations of endo-and exohedral C60 fullerene complexes with Li+ ion and the endohedral C60 fullerene complex with Li2 dimer

The results of ab initio Hartree-Fock calculations of endo-and exohedral C₆₀ fullerene complexes with the Li⁺ ion and Li₂ dimer are presented. The coordination of the Li⁺ ion and the Li₂ dimer in the endohedral complexes and the coordination of Li⁺ ion in the exohedral complex of C₆₀ fullerene are determined by the geometry optimization using the 3–21G basis set. In the endohedral Li⁺C₆₀ complex, the Li⁺ ion is displaced from the center of the C₆₀ cage to the centers of carbon hexa-and pentagons by 0.12 nm. In the Li₂ dimer encapsulated inside the C₆₀ cage, the distance between the lithium atoms is 0.02 nm longer than that in the free molecule. The calculated total and partial one-electron densities of states of C₆₀ fullerene are in good agreement with the experimental photoelectron and X-ray emission spectra. Analysis of one-electron density of states of the endohedral Li⁺@C₆₀ complex indicates an ionic bonding between the Li atoms and the C₆₀ fullerene. In the Li⁺C₆₀ and Li⁺@C₆₀ complexes, there is a strong electrostatic interaction between the Li⁺ ion and the fullerene.     

Production of anti-fullerene C<Subscript>60</Subscript> polyclonal antibodies and study of their interaction with a conjugated form of fullerene

The aim of this study was to produce anti-fullerene C₆₀ antibodies for the development of detection systems for fullerene C₆₀ derivatives. To produce anti-fullerene C₆₀ antibodies, conjugates of the fullerene C₆₀ carboxylic derivative with thyroglobulin, soybean trypsin inhibitor, and bovine serum albumin were synthesized by carbodiimide activation and characterized. Immunization of rabbits by the conjugates led to the production of polyclonal anti-fullerene antibodies. The specificity of the immune response to fullerene was investigated. Indirect competitive immunoenzyme assay was developed for the determination of conjugated fullerene with detection limits of 0.04 ng/mL (calculated for coupled C₆₀) and 0.4 ng/mL (accordingly to total fullerene–protein concentration).     

Photoinduced C70 radical anions in polymer:fullerene blends

Photoinduced polarons in solid films of polymer:fullerene blends were studied by photoluminescence (PL), photoinduced absorption (PIA) and electron spin resonance (ESR). The donor materials used were P3HT and MEH‐PPV. As acceptors we employed PC₆₀BM as reference and various soluble C₇₀‐derivates: PC₇₀BM, two different diphenylmethano‐[70]fullerene oligoether (C₇₀‐DPM‐OE) and two dimers, C₇₀–C₇₀ and C₆₀–C₇₀. Blend films containing C₇₀ revealed characteristic spectroscopic signatures not seen with C₆₀. Light‐induced ESR showed signals at g ≥ 2.005, assigned to an electron localized on the C₇₀ cage. The formation of C₇₀ radical anions also leads to a subgap PIA band at 0.92 eV, hidden in the spectra of C₇₀‐based P3HT and MEH‐PPV blends, which allows for more exact studies of charge separated states in conjugated polymer:C₇₀ blends. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystalline complexes of fullerene with anisole derivatives

For the first time, bis(anisole)chromium fulleride (PhOMe)₂Cr^+·[C₆₀]^−· and a crystalline complex of fullerene with ortho-butoxyanisole have been obtained. The temperature dependence of the parameters of the EPR spectrum of bis(anisole)chromium fulleride (PhOMe)₂Cr^+·[C₆₀]^−· has been studied. The molecular structure of the complex of fullerene with ortho-butoxyanisole has been established.     

Cycloaddition of 2′-azidoethyl glycosides to fullerene[C60] under ultrasonic irradiation

The reactions of fullerene[C₆₀] with 2′-azidoethyl 2,3,4,6-tetra-O-acetyl-α-d-mannopyranoside (2a) and 2′-azidoethyl 2,3,4,6-tetra-O-acetyl-β-d-galactopyranoside (2b) under ultrasonic irradiation cause the cycloaddition of 2′-azidoethyl glycosides to fullerene[C₆₀] and lead to d-glycosyl fullerene[C₆₀] derivatives 3a and 3b, respectively. The glycosyl fullerene[C₆₀] derivatives were characterized by ¹H and ¹³C NMR, UV–vis, FAB-MS, FT-IR spectra and were a 1:1 glycoside fullerene [C₆₀]-adduct.     

Determination of the reaction rate constant and activation energy for pressure-induced 2+2 cycloaddition of the C60 fullerene

The kinetics of fullerene solid-phase dimerization proceeding through the 2+2 cycloaddition of C₆₀ at a pressure of 1.5 GPa is investigated by vibrational spectroscopy in the temperature range 373–473 K. Kinetic curves for the formation of (C₆₀)₂ dimers are obtained using the analytical band at 796 cm^?1 in the IR spectra of the (C₆₀)₂ dimer molecule. Under the assumption that the pressure-induced dimerization of C₆₀ is an irreversible second-order reaction, the reaction rate constants are determined at different temperatures. The activation energy and the preexponential factor are found to be equal to 134±6 kJ/mol and (1.74±0.24)×10¹⁴ s^?1, respectively.     

Processing of C<Subscript>60</Subscript> thin films by Matrix-Assisted Pulsed Laser Evaporation (MAPLE)

Thin films of fullerenes (C₆₀) were deposited onto silicon using matrix-assisted pulsed laser evaporation (MAPLE). The deposition was carried out from a frozen homogeneous dilute solution of C₆₀ in anisole (0.67 wt%), and over a broad range of laser fluences, from 0.15 J/cm² up to 3.9 J/cm². MAPLE has been applied for deposition of fullerenes for the first time and we have studied the growth of thin films of solid C₆₀. The fragmentation of C₆₀ fullerene molecules induced by ns ablation in vacuum of a frozen anisole target with C₆₀ was investigated by matrix-assisted laser desorption/ionization (MALDI). Our findings show that intact fullerene films can be produced with laser fluences ranging from 0.15 J/cm² up to 1.5 J/cm².     

Interfacial electronic structure of molybdenum oxide on the fullerene layer,a potential hole-injecting layer in inverted top-emitting organic light-emitting diodes

The interfacial electronic structures of molybdenum oxide (MoO_x) deposited on fullerene (C₆₀) which could be used as a hole-injecting layer in inverted top-emitting organic light-emitting diodes (TE-OLEDs) were investigated by photoemission spectroscopy. The hole-injecting barrier height (Φ_B^h) at each interface investigated by an ultraviolet photoemission spectroscopy was reduced to from 1.4 to 0.1 eV as the thickness of MoO_x (Θ_MoOx) was increased from 0.1 to 5.0 nm on C₆₀. In these interface system, the sign of vacuum-level shift, highest occupied molecular orbital (HOMO)-level shift, and core-level shifts were all positive indicating that the interface mechanism is attributed to the work-function differences due to a band bending at these interfaces. Moreover, the near-edge X-ray absorption fine structure spectra at carbon K-edge did not show any structural modification as well as any chemical reaction at the MoO_x-on-C₆₀ interfaces when Θ_MoOx was changed on C₆₀. From these results, the inverted TE-OLED with C₆₀ (5.0 nm)/MoO_x (5.0 nm) showed the power efficiency of 1.7 lm/W at a luminance of about 1000 cd/m² and the maximum luminance of about 76.000 cd/m² at the bias voltage of 11.0 V. It exhibited the highest performance among the inverted TE-OLEDs fabricated as a function of MoO_x thickness from 0 to 5.0 nm.     

C<Subscript>60</Subscript> fullerene as an η<Superscript>6</Superscript> ligand in π complexes of transition metals

The possible existence of complexes formed by the C₆₀ fullerene or its derivatives with transition metals interacting with the carbon cage via η⁶−π type bonding is discussed. The derivatives C₆₀ R ₆ of the C₆₀ fullerene (R = −, H, F, Cl, Br, CN) are analyzed using the density functional method within the Perdew-Burke-Ernzerhof approximation. In these molecules, the R groups are attached to carbon atoms located in the α positions with respect to the common hexagon of the C₆₀ fullerene. The structure and electron configuration of complexes formed by these molecules with Cr(C₆H₆), Cr(CO)₃, MoC₆H₆, and Mo(CO)₃ particles are modeled. The “dimer” systems C₆₀R₆-M-R ₆C₆₀ (M = Cr, Mo, R =-, H, F) are investigated in which two fullerene molecules interact via a transition-metal atom. It is found that the introduction of six R groups in the α sites with respect to the common hexagon of C₆₀ favors the formation of complexes of these derivatives of the C₆₀ fullerene with the Cr(C₆H₆), Cr(CO), Mo(C₆H₆), and Mo(CO)₃ particles in which η⁶-π type bonds arise between the metal and the atoms of the hexagon fringed with the R groups. It is also demonstrated that analogous complexes with a “bare” C₆₀ fullerene are possible, but they are significantly less stable. The (C₆H₆) M-R ₆C₆₀ R ₆-M (C₆H₆) complexes of particles M(C₆H₆) (M= Cr, Mo) and derivatives R ₆C₆₀ R ₆ (R =-, H, F, Cl, Br) are studied. In the R ₆C₆₀ R ₆ molecule, six R groups are located in the α sites with respect to the common hexagon of the C₆₀ fullerene and six other groups fringe the opposite hexagon. The obtained results can be applied to planning synthesis of new complexes that C₆₀ fullerene derivatives can form with transition metals. Original Russian Text ￠ E.G. Gal’pern, A.R. Sabirov, I.V. Stankevich, 2007, published in Fizika Tverdogo Tela, 2007, Vol. 49, No. 12, pp. 2220–2223.     

The compressive mechanical properties of Cn (n=20, 60, 80, 180) and endohedral M@C60 (M=Na,Al, Fe) fullerene molecules

The compressive mechanical properties of C_n (n = 20, 60, 80, 180) and endohedral M@C₆₀ (M = Na, Al, Fe) fullerene molecules are investigated using a quantum molecular dynamics (QMD) technique. Energy–strain curves, force–strain curves, endurance load, failure strain corresponding to the endurance load, and compressive stiffness of the fullerene molecules are obtained. The compressive mechanical properties of C₂₀, C₆₀, C₈₀, C₁₈₀ and M@C₆₀ (M = Na, Al, Fe) are discussed. The results show that the larger the magic number n of an empty fullerene, the higher its endurance load and compressive stiffness, but the lower its failure strain, and comparing to the empty C₆₀ fullerene, all the M@C60 molecules have greater endurance capability and failure strain.     

Interaction of sodium fullerene derivatives with trimethylchlorosilane

Soluble dimer compounds of the general formula [C₆₀(Me ₃Si)_n]₂ (where n = 3, 5, 7, or 9 and M _e = CH₃) and a soluble monomer compound, C₆₀(Me ₃Si)₁₂, are synthesized by the reaction of the compound C₆₀Na_n(THF)_x (where n = 4, 6, 8, 10, or 12 and THF = tetrahydrofuran) with trimethylchlorosilane Me ₃SiCl. The compounds synthesized are identified using IR and NMR spectroscopy and mass spectrometry. An irreversible endothermic effect exhibited by the [C₆₀(Me ₃Si)₇]₂ compound in the temperature range 448–570 K is revealed by dynamic adiabatic calorimetry. From analyzing the experimental results, it becomes possible for the first time to demonstrate the structural flexibility of the fullerene in the following sequence of reactions: $\begin{array}{*{20}c} {C_{60} \xrightarrow[{ - 12C_{10} H_8 }]{{ + 12NaC_{10} H_8 }}C_{60} Na_{12} \xrightarrow[{ - 12NaCl}]{{ + excess Me_3 SiCl}}C_{60} (Me_3 Si)_{12} \xrightarrow[{ - 12Me_3 SiCl}]{{ + HCl(gas)}}[C_{60} H_n ]\xrightarrow[{ - 1/2nH_2 }]{{hv}}C_{60} } \\ {C_{60} \xrightarrow[{ - 8C_{10} H_8 }]{{ + 8NaC_{10} H_8 }}C_{60} Na_8 \xrightarrow[{ - 8NaCl}]{{ + excess Me_3 SiCl}}[C_{60} (Me_3 Si)_7 ]_2 \xrightarrow{{573K}}\begin{array}{*{20}c} {products of the} \\ {transformation of + } \\ {Me_3 Si groups} \\ \end{array} C_{60^ - } } \\ \end{array} $      

Simulation of the thermal fragmentation of fullerene C60

Defect formation and annealing processes in fullerene C₆₀ at T = (4000–6000) K are studied using molecular dynamics with a tight-binding potential. The cluster lifetime until fragmentation, which proceeds, as a rule, through the loss of a C₂ dimer, has been found as a function of temperature. The activation energy and the frequency factor in the Arrhenius equation for the fragmentation rate have been found to be E _a = (9.2 ± 0.4) eV and A = (8 ± 1) × 10¹⁹s^?1. It is shown that fragmentation can occur already after the C₆₀ cluster loses its spherical shape. This fact must be taken into account in theoretical calculations of E _a.     

Production and decay of highly-charged fullerene ions

Highly-charged fullerene ions C ₆₀ ^z+ and C ₇₀ ^z+ with charge states up to z=7 have been produced in an electron impact ion source of a two sector field mass spectrometer by using ion source operating conditions similar to those used in EBIT sources. The stability of these ions was investigated quantitatively in the two field free regions of the mass spectrometer. It was found that besides C₂ evaporation the dominant fission process for ions with charges larger than +2 is the loss of a charged C ₂ ⁺ unit via a super-asymmetric charge separation reaction C ₆₀ ^z+ C ₅₈ ^(z–1)+ +C ₂ ⁺ and C ₇₀ ^z+ C ₆₈ ^(z–1)+ +C ₂ ⁺ , respectively. The most important finding from these studies is that this super-asymmetric dissociation reaction proceeds via a three stage reaction sequence involving an electron transfer reaction at the second stage between a receding C₂ unit and the remaining highly-charged fullerene cage.Based on a lecture given by S. Matt at the 1st Euroconference on Atomic Physics with Stored Highly Charged Ions, Heidelberg, 1995.     

Formation of higher-order fullerene dianions in collisions with Na atoms

We have measured electron capture cross sections in collisions between higher order fullerene anions C_n ^- (n=76, 78, 82, 84, 86, 90 and 96) and Na atoms. The ions were produced in an electrospray ion source (ESI) and accelerated to an energy of 50 keV. The measured cross section for dianion formation is three times larger for C₉₆ than that for C₆₀. The latter cross section was earlier found to be 36 ?². The dramatic increase of the cross section with fullerene size is explained by means of the curve crossing model for electron transfer.     

C60 fullerene binding to DNA

Fullerenes have attracted considerable attention in various areas of science and technology. Owing to their exceptional physical, chemical, and biological properties, they have many applications, particularly in cosmetic and medical products. Using the Lennard-Jones 6-12 potential function and the continuum approximation, which assumes that intermolecular interactions can be approximated by average atomic surface densities, we determine the binding energies of a C₆₀ fullerene with respect to both single-strand and double-strand DNA molecules. We assume that all configurations are in a vacuum and that the C₆₀ fullerene is initially at rest. Double integrals are performed to determine the interaction energy of the system. We find that the C₆₀ fullerene binds to the double-strand DNA molecule, at either the major or minor grooves, with binding energies of ?4.7 eV or ?2.3 eV, respectively, and that the C₆₀ molecule binds to the single-strand DNA molecule with a binding energy of ?1.6 eV. Our results suggest that the C₆₀ molecule is most likely to be linked to the major groove of the dsDNA molecule.     

Stoichiometric synthesis of fullerene compounds with lithium and sodium and analysis of their IR and EPR spectra

A modified method is proposed for preparing fullerene compounds with alkali metals in a solution. The compounds synthesized have the general formula Me _n C₆₀(THF)_x, where Me = Li or Na; n=1–4, 6, 8, or 12; and THF = tetrahydrofuran. The use of preliminarily synthesized additives MeC₁₀H₈ makes it possible to prepare fullerene compounds with an exact stoichiometric ratio between C ₆₀ ^n? and Me ⁺. The IR and EPR spectra of the compounds prepared are analyzed and compared with the spectra of their analogs available in the literature. The intramolecular modes T _u (1)-T _u (4) for the C ₆₀ ^n? anion are assigned. The splitting of the T _u (1) mode into a doublet at room temperature for Me _n C₆₀(THF)_x (n=1, 2, 4) compounds indicates that the fullerene anion has a distorted structure. An increase in the intensity of the T _u (2) mode, a noticeable shift of the T _u (4) mode toward the long-wavelength range, and an anomalous increase in the intensity of the latter mode for the Li₃C₆₀(THF)_x complex suggest that, in the fullerene anion, the coupling of vibrational modes occurs through the charge-phonon mechanism. The measured EPR spectra of lithium-and sodium-containing fullerene compounds are characteristic of C ₆₀ ^? anions. The g factors for these compounds are almost identical and do not depend on temperature. The g factor for the C ₆₀ ^n? anion depends on the nature of the metal and differs from the g factor for the C ₆₀ ^? anion.