Solution ozonolysis of C<Subscript>70</Subscript>: stable products and chemiluminescence

For the first time the total and relative contents of the stable ozonolysis products of fullerene C₇₀ solutions were identified by IR spectroscopy and elemental and chemical analyses. At the 100% conversion of C₇₀ a mixture of products corresponding to the empirical formula C₇₀O_14.3H_0.21 (epoxides: polyketones: polyesters: secondary fullerene ozonides (SFOZ): acids = 1.07: 6: 6: 0.21: 1.02) is formed. The content of polyketones, polyesters, acids, and SFOZ increases during the whole ozonolysis time (1 h). The number of oxygen atoms in epoxides C₇₀O _n (n = 1–4) is lower than that in epoxides C₆₀O _n (n = 1–6) formed by the ozonolysis of fullerene C₆₀. The kinetic curve of accumulation of epoxides C₇₀O _n (n = 1–4) passes through a maximum, which is observed 0.5 min after the beginning of ozonolysis. No epoxides were identified among the products 3.5 min after the ozonolysis. The photoluminescence (PL) (λ_max = 645 and 685 nm) of fullerene polyketones in glassy EtO₂/EtOH solutions frozen at 77 K was observed. This PL is much brighter, than that of polyketones formed upon the ozonolysis of fullerenes C₆₀. For the first time the chemiluminescence (CL) was detected and studied upon the ozonolysis of C₇₀ solutions at 300 K. The CL emitters are excited states of fullerene polyketones. The CL spectrum is partially overlapped with the known CL spectrum appeared upon the ozonolysis of C₆₀ (λ_max = 685 nm) but contains the greater number of maxima (λ_max = 645 and 685 nm), which is related to a lower symmetry of the C₇₀ oxidation products.     

The structural-phase state of C<Subscript>60</Subscript>-C<Subscript>70</Subscript> fullerene mixtures

The structural and phase state of the C₆₀-C₇₀ system at various C₆₀/C₇₀ ratios in mixtures obtained by the vaporization of solutions in toluene at ∼98°C was studied by X-ray structure analysis, differential scanning calorimetry, and infrared spectroscopy. Solid solutions based on the face-centered cubic packing of C₆₀ are not formed in the C₆₀-C₇₀ system at C₇₀ contents from 0.5 to 50 wt %. The hexagonal close packing of a solid solution of C₆₀ in C₇₀ can be formed as a result of the thermally activated decomposition of the ternary crystal solvate in the C₆₀-C₇₀-C₆H₅CH₃ system. The structural state of multiphase mixtures formed under conditions far from equilibrium is characterized by a high degree of structure imperfection and greater ability to undergo oxidation compared with C₆₀ and C₇₀.     

Mass spectrometric determination of the electron affinity of C<Subscript>60</Subscript>(CF<Subscript>3</Subscript>)<Subscript>10</Subscript> and C<Subscript>60</Subscript>(CF<Subscript>3</Subscript>)<Subscript>12</Subscript> molecules

Knudsen cell mass spectrometry was used to study ion-molecular electron exchange reactions between some trifluoromethyl derivatives of C₆₀ fullerene. Electron affinity values were experimentally determined for C₆₀(CF₃)₁₀ and the S ₆ isomer of C₆₀(CF₃)₁₂ and compared with the results of calculations and the data in the literature.     

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.     

Circular dichroism of optically active organometallic derivatives of fullerenes C<Subscript>60</Subscript> and C<Subscript>70</Subscript>

Palladium and platinum complexes of fulleienes C₆₀ and C₇₀ containing the axially chiral ligand (—)-BITIANP (BITIANP is 2,2’-bis(diphenylphosphino)-3,3’-bi(benzo[b]thiophene)) and pynolidino[60]fullerene bearing a planar chiral organometallic π-complex substituent in the heteiocyclic ring were studied by circular dichroism (CD) spectroscopy.     

Electrochemical properties of transition metal complexes with C<Subscript>60</Subscript> and C<Subscript>70</Subscript> fullerne ligands (review)

t-The electrochemical properties of exohedral complexes of transition metals with metallofragments coordinated to C₆₀ and C₇₀ fullerene ligands in different coordination modes are surveyed. The effect of the nature, composition, and structure of metal-containing fragments on the electrochemical properties of these complexes and stability of products formed in the oxidation and reduction of complexes is discussed.     

Synthesis of fullerene C<Subscript>60</Subscript> monoadducts. Cyclopropanation of C<Subscript>60</Subscript> with sulfonium ylides

3′H-Cyclopropa[1,9](C₆₀-I_h)[5,6]fullerene-3′-carboxylic acid can be synthesized in a good yield by cyclopropanation of fullerene C₆₀ with 2-(dimethyl-λ⁴-sulfanylidene)acetates provided that the ester residue is readily hydrolyzable in acid medium.     

Synthesis and structures of C<Subscript>60</Subscript> fullerene chlorides

Systematic study of chlorination of fullerene C₆₀ with inorganic chlorides SbCl₅, VCl₄, MoCl₅, and KICl₄ was carried out. Higher chlorofullerenes, viz., T _h -C₆₀Cl₂₄, C₆₀Cl₂₈, C ₂-C₆₀Cl₃₀, and D _3d -C₆₀Cl₃₀, can be prepared depending on the temperature and time of chlorination. The molecular and crystal structures of C₆₀Cl₂₄⋅VOCl₃, C₆₀Cl₃₀⋅2CS₂, and C₆₀Cl₃₀O_1.22 were determined by single-crystal X-ray diffraction. Fullerenes C₆₀Cl₂₈ and C ₂-C₆₀Cl₃₀ were shown to be only kinetically stable, whereas D _3d -C₆₀Cl₃₀ is a thermodynamically stable product. Transformations of less chlorinated fullerenes into more chlorinated products are accompanied by substantial changes in the addition patterns. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1608–1618, July, 2005.     

Endohedral Complex of Fullerene C<Subscript>60</Subscript> with Tetrahedral N<Subscript>4</Subscript>, N<Subscript>4</Subscript>@C<Subscript>60</Subscript>

B3LYP/6-31G(d) hybrid HF/DFT and BLYP/6-31G(d, p) DFT calculations were carried out to determine the structural and electronic properties of the endohedral complex of C₆₀ with Tetrahedral N₄ (T_d N₄), N₄@C₆₀. It was demonstrated that N₄ was seated in the center of the fullerene cage and the tetrahedral structure of N₄ is remained in the cage. The formation of this complex is endothermic with inclusion energy of 37.92 kcal/mol. N₄ endohedral doping perturbs the molecular orbitals of C₆₀ not so much, the calculated HOMO–LUMO gaps, the electron affinity (EA) and the ionizational potential (IP) of N₄@C₆₀ are similar to that of C₆₀.     

Synthesis and structure of allylated derivatives of fullerenes C<Subscript>60</Subscript> and C<Subscript>70</Subscript>

New chromatographically pure monoand hexamethanofullerenes C₆₀ and C₇₀ containing active allylic groups were synthesized by Bingel—Hirsch reaction. These compounds are promising for the studies of biological activity, as well as for obtaining on their basis new fullerenecontaining materials. The purity and composition of the synthesized compounds were confirmed by MALDI-TOF mass spectrometry and HPLC, their structure was established by ¹H and ¹³C NMR spectroscopy and X-ray diffraction.     

Photophysical Investigations on Determination of Ionicity and Electronic Structures for the Non-covalent Complexes of Calix[4]resorcinarene with Fullerenes C<Subscript>60</Subscript> and C<Subscript>70</Subscript> in the Solution State

Ground state non-covalent interactions between a macrocyclic receptor, C-methylcalix[4]resorcinarene (1) and fullerenes (C₆₀ and C₇₀) have been studied in benzonitrile by an absorption spectrophotometric method. Absorption bands are located in the visible region due to the charge transfer (CT) transition between 1 and various electron acceptors (including fullerenes), namely, 2,3-dichloro-5,6-dicyano-p-benzoquinone, tetracyanoquinodimethane and p-chloranil. Utilizing the CT absorption bands, various important physicochemical parameters, including oscillator strength, resonance energy, transition dipole strength of all the acceptor-1 complexes and vertical ionization potential of 1 are determined. Job’s method of continuous variation reveals 1:1 stoichiometry between fullerenes and 1. The most fascinating feature of the present study is that 1 binds selectively to C₇₀ compared to C₆₀ as obtained from binding constant (K) data of C₆₀-1 (K_C60-1K_{\mathrm{C}60\mbox{-}\mathbf{1}}) and C₇₀-1 (K_C70-1K_{\mathrm{C}70\mbox{-}\mathbf{1}}) complexes, i.e., K_C60-1=190K_{\mathrm{C}60\mbox{-}\mathbf{1}}=190 dm³⋅mol⁻¹ and K_C70-1=5,800K_{\mathrm{C}70\mbox{-}\mathbf{1}}=5{,}800 dm³⋅mol⁻¹ and selectivity (K_C70-1 /K_C60-1 ) ∼30. Quantum chemical calculations based on hybrid density functional theory estimate the enthalpies of formation of the fullerene-1 complexes in vacuo and provide very good support for selectivity in the K values of the C₇₀ and C₆₀ complexes of 1. The exchange and correlation energies have been calculated using a hybrid DFT functional method. We have opted to use the hybrid DFT functional over the Hartree-Fock method, as it can account for correlation effects also. Molecular electrostatic potential map calculations give a clear picture on the electronic structures of the fullerene-1 complexes.     

Sorption of light fullerenes C<Subscript>60</Subscript> and C<Subscript>70</Subscript> on NORIT-AZO carbon

Sorption of fullerenes C₆₀ and C₇₀ from o-xylene, toluene, and dichlorobenzene solutions on NORIT-AZO carbons was studied.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 10, 2004, pp. 1638–1642.Original Russian Text Copyright © 2004 by Semenov, Seregin, Arapov, Charykov.     

Influence of UV Pretreatment on Thermooxidative Degradation of Poly(Methyl Methacrylate) Films with Fullerene C<Subscript>60</Subscript> or C<Subscript>70</Subscript>

Wariation of the concentration of fullerenes C₆₀ and C₇₀ in poly(methyl methacrylate) films under UV exposure in atmospheric oxygen was studied. The mechanism of the influence exerted by addition of some photostabilizing polymers and xanthene dyes on the photooxidative degradation of fullerene in the polymer matrix was analyzed.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 6, 2005, pp. 1038–1042.Original Russian Text Copyright © 2005 by Troitskii, Khokhlova, Konev, Denisova, Novikova, Lopatin.     

Generation of fullerenyl radicals and chemiluminescence in the (C<Subscript>60</Subscript>—R<Subscript>3</Subscript>Al)—O<Subscript>2</Subscript> system

Fullerenyl radicals (FR) RC₆₀ ^· and chemiluminescence (CL) are generated in the presence of O₂ in C₆₀—R₃Al (R = Et, Buⁱ) solutions in toluene (T = 298 K). The FR are formed due to the addition of the R^· radical, which is an intermediate of R₃Al autooxidation, to C₆₀. Mass spectroscopy and HPLC were used to identify Et_nC₆₀H_m (n, m = 1–6), Et_pC₆₀ (p = 2–6), and dimer EtC₆₀C₆₀Et as stable products of FR transformations. As found by ESR, the EtC₆₀ ^· radical (g = 2.0037) is also generated by photolysis of solutions obtained after interaction in the (C₆₀— R₃Al)—O₂ system. In the presence of dioxygen, the FR is not oxidized but yields complexes with O₂, which appear as broadening of the ESR signals. Chemiluminescence arising in the (C₆₀—R₃Al)—O₂ system is much brighter (I _max = 1.86·10⁸ photon s⁻¹ mL⁻¹) than the known background CL (I _max = 6.0·10⁶ photon s⁻¹ mL⁻¹) for the autooxidation of R₃Al and is localized in a longer-wavelength spectral region (λ_max = 617 and 664 nm). This CL is generated as a result of energy transfer from the primary emitter ³CH₃CHO* to the products of FR transformation: R_nC₆₀H_m, R_pC₆₀, and EtC₆₀C₆₀Et. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 205–213, February, 2007.     

Octafluorocyclohexa derivatives of [60]fullerene: C<Subscript>60</Subscript>(C<Subscript>4</Subscript>F<Subscript>8</Subscript>)<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> (<Emphasis Type="Italic">n</Emphasis> = 2, 3, 4, and 6)

Fluorocyclohexa adducts C₆₀(C₄F₈) _n were synthesized by high-temperature reaction of fullerene C₆₀ with 1,2-C₂F₄I₂ or 1,4-C₄F₈I₂ in sealed tubes. Their separation by HPLC allowed us to determine molecular structure (X-ray diffraction) of four new compounds C₆(C₄F₈) _n (n = 2, 3, 4, and 6). Structures of isomers C₆₀(C₄F₈) _n were discussed in terms of a concept of consecutive addition of C₄F₈ groups to the fullerene cage.     

A Quantum Chemical Study of C<Subscript>60</Subscript>Cl<Subscript>30</Subscript>, C<Subscript>60</Subscript>(OH)<Subscript>30</Subscript> Molecules and Fe@C<Subscript>60</Subscript>(OH)<Subscript>30</Subscript> Endocomplex

(U)PBE0/cc-pVDZ method is used to study the structure of C₆₀Cl₃₀, C₆₀(OH)₃₀ molecules and Fe@C₆₀(OH)₃₀ endocomplex. The triplet state of the endocomplex is shown to be the lowest in energy among its four states corresponding to different spin multiplicities and positions of Fe nucleus within the fullerene cavity. This state is characterized by bonding between the iron atom and one of two benzenoid cycles of the carbon cage, six internuclear Fe–C distances (208 pm), and 1s²2s²2p⁶3s²3p⁶3d^7.24s^0.14p^0.3 electron configuration of iron with spin population of 2.36.     

Catalytic cycloaddition of diazoalkanes with heterocyclic substituents to fullerene C<Subscript>60</Subscript>

Methanofullerenes were directly synthesized under mild conditions by cycloaddition to fullerene C₆₀ of diazoalkanes generated in situ by oxidation of ketone hydrazones containing a heterocyclic fragment with manganese(IV) oxide in the presence of the catalytic system Pd(acac)₂-2 PPh₃-4 Et₃Al.     

The saturated hydrides of C<Subscript>60</Subscript>:F<Subscript>5</Subscript>F<Subscript>6</Subscript> PK F<Subscript>5</Subscript>F<Subscript>7</Subscript> isomers

The carbon cages composed of pentagons and heptagons (F₅F₇ isomers) are the analogs of fullerenes composed of pentagons and hexagons (F₅F₆ isomers). To provide insight into the structures and stability of the hydrides of F₅F₆ and F₅F₇ isomers, systematical density functional theory calculations are performed on all the 1,812 F₅F₆–C₆₀H₆₀ and 56 F₅F₇–C₆₀H₆₀. The calculated results demonstrate that the isomer with lowest/highest energy has most/fewest fused pentagons for both F₅F₆ and F₅F₇ hydrides and the stability of these hydrides increase with the number of fused pentagons roughly. The lowest energy F₅F₆–C₆₀H₆₀ and F₅F₇–C₆₀H₆₀ are 237.1 and 152.5 kcal/mol lower in energy than the isolated pentagon rule (IPR) C₆₀H₆₀, respectively; however, these two parent cages are 529.6 and 660.0 kcal/mol higher in energy than the IPR C₆₀. The calculations suggest that heptagon-containing cages, not only those violating the IPR can be the candidate cages for fullerene derivatives and the possible repulsion between the added atoms may play an important role in determining the structures and stability of the hydrides of carbon cages.     

The standard enthalpy of formation of fullerene chloride C<Subscript>60</Subscript>Cl<Subscript>30</Subscript>

A rotating-bomb calorimeter was used to measure the energy of combustion of crystalline fullerene chloride C₆₀Cl₃₀ · 0.09Cl₂, Δ_c U° = (?24474 ± 135 kJ/mol). The result was used to calculate the standard enthalpy of formation, Δ_f H° (C₆₀Cl₃₀, cr) = 135 ± 135 kJ/mol, and the C-Cl bond energy, 195 ± 5 kJ/mol. The C-X (X = F, F, Cl, and Br) bond energies in fullerene C₆₀ derivatives and other organic compounds are compared.     

Sorption of Light Fullerenes (C<Subscript>60</Subscript> and C<Subscript>70</Subscript>) on Materials Prepared by Sublimation of Graphite Rods

Sorption of fullerenes C₆₀ and C₇₀ from o-xylene, toluene, and o-dichlorobenzene solutions under static conditions on a sorbent prepared by sublimation of graphite rods was studied. The sorption isotherms of both fullerenes at 25°C were measured.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 2, 2005, pp. 345–346.Original Russian Text Copyright © 2005 by Semenov, Arapov, Charykov, Nekrasov, Alekhin, Gerasimov, Seregin.