Near-Infrared Laser-Induced Decomposition of C60 Dissolved in Toluene

Abstract

In this paper we describe the efficient and substantial decomposition of C₆₀ in toluene solution, induced by moderate intensity (I = 20 - 55 MW cm^?2) near infrared (γ = 1064 nm) laser radiation. This behavior is surprising since both uncharged fullerene and toluene do not have any absorption bands at this wavelength. The decomposition efficiency and products are investigated with UV-Vis absorption spectrophotometry and high-performance liquid-chromatography (HPLC). Possible mechanisms of the fullerene decomposition are discussed.     

Radiation-Induced Synthesis of Fullerene-Silica Hybrid Nanomaterials

C₆₀ fullerene has been radiation grafted on bare and functionalized silica surface with mercaptopropyl moieties in toluene solution. The resulting fullerene-silica hybrid nanomaterials have been characterized by FT-IR and solid state ¹³C CP-MAS NMR spectroscopy and compared to the radiolysis products of C₆₀ in toluene. It has been found that fullerene is grafted on silica surface but, because the radiation grafting has been conducted in toluene, fullerene results arylated from radicals derived from toluene radiolysis. The fullerene-silica hybrid nanomaterials cannot be extracted by warm decalin, demonstrating that the fullerene cage is chemically bonded on the silica surface. The thermal behavior of fullerene-silica hybrid nanomaterials has been studied by thermogravimetric analysis (TGA) and differential thermal analysis (DTA) in air flow.     

CO-DEPOSITION OF FULLERENES AND SULFUR FROM DILUTED SOLUTION

A new method to synthesize fullerene and sulfur compounds has been developed. Using this method, C₆₀S₁₆ and C₇₀S₁₆ compounds were grown from dilute fullerene and sulfur toluene solution. Their atomic structures were analyzed by x-ray diffraction with the single crystal. The C₆₀S₁₆ crystal is C-centered monoclinic structure of a=2.0874 nm, b=2.1139 nm, c=1.05690 nm and β=111.93°, and the C₇₀S₁₆ has a primitive monoclinic, P2₁/c, with lattice parameters of a=1.5271 nm, b=1.49971 nm, c=2.18024 nm and β=109.791°. In this compound, the structure of fullerenes is maintained and sulfur atoms form S₈ rings placed around the fullerenes.     

Synthesis and Characterisation of Some New Ferrocenyl- and Ferrocenylalkynyl-[60]Fullerene Compounds

We report the synthesis and characterisation of a series of ferrocenylfullerene compounds, and some new ferrocene derivatives required as intermediates. The new fullerene species are Fc-[60]fullerene, (8); Fc-C=C-[60]fullerene, (10); Fc-C=C-C=C-[60]fullerene, (12); and (η-C₅H₄SiBu₃)Fe(η-C₅H₄)-[60]fullerene, (14).     

Arylation of [60]Fullerene with Br2/FeCl3/PhH: Formation of C58 Derivatives via CO Loss

Heating a mixture of [60]fullerene, bromine, ferric chloride and benzene under reflux for 24 h products a range of phenylated [60]fullerene derivatives. The main product is C₆₀Ph₅H but other components identified by mass spectrometry (and in some cases separated by HPLC) are: C_6oPh_n(n = 4, 6, 8, 10, 12), C₆₀Ph_nO₂(n = 4, 6, 8, 10, 12), C₆₀Ph_nOH (n = 7, 9, 11), C₆₀Ph_nH₂ (n = 4, 10), C₆₀Ph₄H₄, C₆₀Ph₅H₃, C₆₀Ph_n0₂H (n = 5, 9), C₆₀Ph₄C₆H₄O₂, C₆₀Ph₉OH₃, and C₆₀Ph₁₁ O₃H₂. In the corresponding reaction with toluene, the crude reaction mixture contained C₆₀(MeC₆H₄)₄ as a main product; C₆₀(ClC₆H₄)₅H was obtained from the reaction with chlorobenzene. Formation of these derivatives is believed to involve radical bromination of the fullerene, followed by electrophilic substitution of the hatogenofullerene into the aromatic, accompanied in some case by hydrolysis, elimination and epoxide formation; oxidation may also introduce ketone/dioxetane functionality. The EI mass spectra of C₆₀Ph₄O₂ and C₆₀Ph₈O₂show degradation to C₅₈Ph_n (n = 0-8), having structures believed to be related to the pseudofollerenes C₆₈Ph_n (n = 0-8) reported recently. These results suggest that some derivatisations of fullerenes confer stability, due to the relief of strain.     

Pyrolytic Trifluoromethylation of [76]-, [78]-, [84]-, and Aza[60]Fullerenes with Silver Trifluoroacetate; Evidence for Coordination of Fullerenes to Silver

Pyrolytic trifluoromethylation of [76], [78], [84], and aza[60]fullerenes with silver trifluoroacetate at 300°C results in extensive polyaddition of up to 18, 18, 20 and 20 CF₃ groups, respectively. In contrast to trifluoromethylation of [60]- and [70]fullerenes that give a full range of derivatives ranging upwards from C_n(CF₃)₂, [76]-, [78]-, and [84]-fullerenes only give C_n(CF₃)_6-18 derivatives, largely in the 10-12 CF₃ range; reaction with [76]fullerene is accompanied by formation of C₆₀(CF₃)₆ attributed to cage fragmentation. For aza[60]fullerene the hexa-addition level dominates, in contrast to its other reactions which give predominantly penta-addition products. All the compounds showed peaks at 1256±2 and 1180-1190 cm^-1, due to the CF₃ group, and peaks in this region are shown also by the soluble extract obtained on trifluoromethylation of nanotubes. As in trifluoromethylation of [60]- and [70]-fullerenes, the products obtained initially are involatile, attributed to formation os silver complexes; these are decomposed on subsequent solution in toluene. Mixed isomeric trifluoromethylated C₆₀F₈ derivatives viz. C₆₀F₇CF₃, C₆₀F₆(FG₃)₂, C₆₀F₅(CF₃)₃ and C₆₀F₄(CF₃)₄, and C₆₀F₄CF₃CF₂CF₃ (a C₆₀F₆ derivative) have been isolated from fluorination of [60]fullerene with MnF₃/K₂NilF₆ at 510°C.     

Preparation and characterization of C60S16 and C70S48 thin films

In this study, we have investigated different methods for preparation of thin films of C₆₀ and C₇₀-sulfur compounds. Films of good quality were obtained by reaction of amorphous C₆₀ and C₇₀ films with a saturated sulfur solution in toluene at 40°C or with saturated sulfur vapour at a temperature of 140°C for several hours. The quality of the fullerene-sulfur films were strongly dependent on the microstructure of the initially deposited fullerene film and the synthesis temperature. X-ray diffraction analyses showed that both methods lead to the formation of films consisting of C₆₀S₁₆ and C₇₀S₄₈ (space groups C 2/c and Amm2, respectively). C₆₀S₁₆ films synthesised on Al₂O₃(012) and Si(100) substrates were texture-free while C₇₀S₄₈ films typically exhibited a preferential (100) orientation. The films were also characterised by Raman and IR- spectroscopy, which confirmed that the interactions between the fullerene molecules and the S₈ rings are weak. The fullerene-sulfur compounds were found to be unstable at high vacuum conditions. Both materials C₆₀S₁₆ and C₇₀S₄₈ are non-conductive at room temperature with conductivities less then 10⁻⁵ (Ω/cm).     

Small-Angle Neutron Scattering and Photon Correlation Spectroscopy Investigation on Buckminsterfullerene Solutions

Small-Angle Neutron Scattering (SANS) and Photon Correlation Spectroscopy (PCS) findings on Buckminsterfullerene (C₆₀) solutions are presented. The analysis of SANS data allows to characterize the shape and to determine the value of the gyration radius of C₆₀ dissolved in CS₂, a solvent capable to guarantee a good contrast for the neutron probe. We obtained information about the conformation of fullerene in solution, and, by means of comparisons with experimental and theoretical data existing in literature, we found a confirmation that the gyration radius R_g is independent on concentration. PCS measurements were performed on fullerene/organic solvents (toluene, chloroform and CCl₄) solutions. Since the diffusion coefficient is related, through the Stokes-Einstein relation, to the scatterer hydrodynamic radius, R_H, we have obtained information about the conformation of fullerene in solution and about the character of the structural and hydrodynamic interaction.     

Synthesis of High-Molecular-Weight [60]Fullerene Pearl-Necklace Polyamides Derived from Equatorial [60]fullerenobisacetic Acid

A series of [60]fullerene pearl-necklace polyamides, consisting of equatorial-[60]fullerenobisacetic acid and various chromophoric aromatic diamines, were synthesized by a phosphorylation route using large amounts of triphenyl phosphite and pyridine as condensing reagents with stepwise addition of the condensing reagents. In the present polymers, [60]fullerene pearls and diamine linkers were attached to one another by cyclopropane connectors. The polyamides had weight-average molecular weights (M_w)of 4.5-5.0×10⁴ g/mol and inherent viscosities (n_inh) of 0.3-0.4 dL/g in N, N-dimethylacetamide (DMAc) at 30 °C. They had glass transition temperatures at 30-125 °C and decomposition temperatures at 300-310 °C. The UV-VIS spectra in DMAc exhibited broad absorption with λ_max at 310-390 nm tailing to longer wavelengths.     

Modifications of Fullerenes Extractions and Chromatographies with Different Solvents

In the Bucky System II, based on electrical arc method, carbon soot was produced. Fullerenes C₆₀ and C₇₀ were Soxhlet extracted from the collected soot samples with toluene, chlorobenzene and with both of them successively, modifying the original methods. The yields of the both obtained toluene extracts were 5.4%. Chlorobenzene extract yield was 5.8%. After extraction of toluene insoluble soot with chlorobenzene, the entire extract yield was increased from 5.4% to 5.8%, due to modification of the existing methods. The difference of fullerenes solubilities in these solvents has been concluded. In the second part of our work toluene and chlorobenzene fullerenes extracts were separated by column chromatographies on active Al₂O₃, modifying the existing methods, by elution with hexane and mixtures of benzene, toluene, or xylene with hexane in determined ratios and orders. Identifications of buckminsterfullerene C₆₀ in the first chromatographically purified fractions were achieved by electron impact ionization (EI) mass, IR, and UV/VIS spectroscopy. The second and the third purified fullerene fractions, toluene and chlorobenzene soot extracts were characterized by IR and UV/VIS methods.     

Synthesis of mono-dispersed nano-scale fullerene (C60) crystals

Fullerene (C60), which has a unique molecular structure, was used in the preparation of crystalline organic nano-crystals. Fullerene was dissolved in toluene and this fullerene solution was mixed with water drastically. During this process, fullerene transferred from toluene to water phase. The significantly different solubility of fullerene in a toluene/water solvent system played an important role in the self-assembly of single fullerene nano-crystals, as it is called drowning-out crystallization. In addition, pH of water was controlled to carry out the interfacial transference of fullerene. An optical spectrum analysis showed that the fullerene was transferred by a hydrolysis reaction from toluene to water, depending on the pH and toluene involved in the crystal structure. During the interfacial transference, the growth of nano-scale fullerene occurred at pH > 7. Importantly, fullerene nanocrystals were formed with a mono-dispersed square structure on a nano-scale (104 nm average size and 1.03 +/- 0.24 aspect ratio) at pH 10.     

CHROMATOGRAPHIC PURIFICATION OF Kr@C60

Unusual compounds have been reported to form by the incorporation of atoms into fullerene cages. The compounds in which a noble gas atom is trapped into a C₆₀ cage are very stable and only van der Waals interactions occur between the noble gas and the fullerene cage. The study of these compounds requires efficient chromatographic (or other) separations. We performed the isolation of Kr@C₆₀ and a study of its chromatographic separations on several HPLC columns using toluene : hexane mixtures as solvent. We found that the separation factor is small (1.09 to 1.12) with the highest separation factor on a Buckyprep column.     

AN FT-ICR STUDY ON LASER ABLATION OF GRAPHITE AND CARBON BLACK TARGETS: COSMOCHEMICAL IMPLICATIONS

Graphite and carbon black samples were laser ablated in an FT-ICR (Fourier transform-ion cyclotron resonance spectrometer) by Nd-YAG laser under high vacuum in conditions recalling those existing in the interstellar medium. It is shown that graphite gives a regular sequence of polyyne and cyclopolyyne chains from C₁₀ to C₂₇ and additionally produces 2% of C₆₀ fullerene. When carbon black is used in place of graphite under the same conditions, no C₆₀ fullerene was produced and also the sequence of polyyne species generated was very irregular. If really carbon black structure and elemental composition approaches more closely than pure graphite the structure of the carbon dust, we can predict that C₆₀ fullerene should not be produced from the thermal decomposition of this dust in high vacuum.     

Synthesis of Fullerenols from Halofullerenes

Halogenated fullerenes were used as reagents to prepare fullerenols. Depending on reaction conditions two types of substances (complex mixtures of products with average compositions C₆₀O_nH_m, n=10-26, m=14-30 and C₆₀O_nH_mM_k, M=K, Na; n=17-24, m=16-28, k=3-8) possessing essentially different water solubility were obtained. Highly soluble metal-containing species are most likely ionic compounds similar to metal derivatives of alcohols-alcoholates. An electron withdrawing effect of the carbon cage could make alkali metal fullerenolates (C₆₀(OH)_x(OM)_y) inert towards hydrolysis. Halogens were selectively substituted when fullerene bromides and chlorides were treated with silver trifluoroacetate. Fullerenol esters C₆₀(OOCCF₃)_n formed were then hydrolyzed to form C₆₀(OOCCF₃)_x(OH)_y. Attempts to cleave all ester groups in C₆₀(OOCCF₃)_x(OH)_y failed in acidic media, while alkaline hydrolysis was accompanied by unselective polyhydroxylation of the fullerene cage.     

Solubility of Fullerene C60 and C70 in Toluene, o-Xylene and Carbon Disulfide at Various Temperatures

The solubilities of fullerene C₆₀ and C₇₀ in toluene, o-xylene and carbon disulfide between the melting point and boiling point of the solvents, respectively, have been measured. The temperature dependent solubility of C₆₀ displays anomalous behaviors. A solubility maximum of C₆₀ around 0 °C for toluene and carbon sulfide and around 30 °C for o-xylene was observed. The temperature-dependent solubility of C₇₀ behaves normally for all the three solvents studied.     

Synthesis and Characterization of Divalent Organolanthanide-Fullerene Adducts Cp2LnC60 (Ln=Yb, Sm): First Example of Insertion Reaction Involving Cyclopentadienyl and Fullerene

Reaction of equimolar amount of Cp₂Ln (Ln=Yb, Sm) with fullerene C₆₀ affords Cp₂LnC₆₀ (Ln=Yb, Sm), and insertion reaction involving cyclopentadienyl and fullerene was reported first time.     

Production and Characterization of (Al, Fe)-C (Graphite or Fullerene) Composites Prepared by Mechanical Alloying

(Al, Fe)-C_graphite and (Al, Fe)-C_fullerene composites have been prepared by mechanical alloying using ball milling of powders. Consolidation has been achieved by a spark plasma sintering technique (SPS). Results of XRD and TEM indicate that pure fullerene withstands milling. SEM results show homogeneous powders after milling but with different morphologies depending on the specific system. Milling produces a fine mixture of Al or Fe and graphite or fullerene. SPS produces a dense material with a nanocrystalline structure. The sintered samples have a metallic matrix (Al or Fe) with a fine dispersion of AI₄C₃ in the case of Al-C_{( graphiteorfullerene)}, Fe₃,C in the case of Fe-C_(graphite), and fullerene in the case of Fe-C _(fullerene), Hardness measurements show that higher values are obtained in the Al-C_(fullerene), and Fe-C_{(graphite )} specimens.     

Ab initio calculation on fullerene C32 and Its Derivative

In this paper, we studied the equilibrium geometries, the electronic structures and the binding energies of fullerene C₃₂ as well as its hydrogenates and fluorides interactions by the SCF Hartree-Fock calculations using the latest version of GAMESS of ab initio programs. The fullerene C₃₂ is found to have a ¹A₂' closed-shell ground state in D_3d symmetry or a ¹E_U singlet state in D_3h symmetry. It is predicted to be easy to add some hydrogen or fluorine atoms to the C₃₂ cage and to produce a series of derivatives C₃₂H_2n,C₃₂F_2n (n=l, 3, 6), in which C₃₂H₂,C₃₂F₂ (D_3d), C₃₂H₆^a,C₃₂F₆^c(D_3h) are more stable. We suggest that this implies that the vertex of triplet pentagons of the C₃₂ cage is an activation site for addition.     

Superconductivity of Organic Materials: Beyond the Fullerenes

We first briefly review the application of the BCS mechanism with electron-phonon interaction to the superconductivity of the A₃C₆₀ compounds. We then explore an extension of this family of compounds by using aromatic cryptands that we consider as “pseudo fullerene molecules”. Preliminary measurements of low field microwave absorption are consistent with superconducting behavior and a Tc ∼ 50K.     

MOLECULAR AND CRYSTAL STRUCTURE OF THE ADDUCTS OF C60F18 WITH AROMATIC HYDROCARBONS

The solubility of C₆₀F₁₈ in aromatic hydrocarbons, benzene, toluene, and xylenes (0.48-1.23 mg/mL), and decomposition enthalpies for the 1 : 1 and 1 : 2 complexes (31-70 kJ/mole) have been determined. The C₆₀F₁₈ molecule has near perfect C_3v symmetry, and the x-ray single-crystal structures of the C₆₀F₁₈ L complexes (L=hexamethylbenzene, o-, m-, p-xylene, and bromobenzene) are compared in terms of 12 types of C-C and four types of C-F bonds. Analysis of the packing modes in the crystals shows an influence of the size and polarity of the aromatic hydrocarbon molecule.