A Study of the Addition of Alkylamines and Hydrazine to Fullerenes

A 1:1 monoadduct of 1-aminobutane with C₆₀, C₆₀(H)(n-C₄H₉NH), has been characterized by mass spectrometry, infrared spectroscopy and other techniques. Addition of 1,4-diaminobutane to C₆₀ gives rise to a 1:2 adduct of the diamine with C₆₀, while hydrazine hydrate gives multiple addition products. Under conditions of diimide reduction, C₆₀ gives products resulting from the addition of hydrazine units as well as reduction.     

聚乙烯亚胺修饰富勒烯的制备及其对聚丙烯热氧稳定性的影响

利用聚乙烯亚胺(PEI)分子中活泼的?NH?与富勒烯(C₆₀)结构中C=C键之间的加成反应,制备了PEI修饰C₆₀杂化物(C₆₀?PEI),并采用FTIR、TEM等测试方法对C₆₀?PEI的分子结构和形态进行表征。采用熔融共混法制备了C₆₀?PEI/聚丙烯(PP)复合材料,并对其热性能和阻燃性能进行研究。热失重分析结果表明,C₆₀?PEI可以更有效地发挥C₆₀的自由基捕捉作用,对PP热稳定性的提高效果较C₆₀更明显;氧化诱导测试(OIT)结果表明,C₆₀?PEI/PP复合材料比C₆₀/PP复合材料具有更优异的抗氧性能;微型量热测试也表明,燃烧过程中C₆₀?PEI/PP复合材料比C₆₀/PP复合材料具有更低的热释放量。      

Some New Aspects of Chlorination of Fullerenes

The effect of the reagent ratio, reaction time and power of the reagent on the product composition in chlorination of [60]fullerene was studied. Chlorofullerenes C₆₀Cl₆, C₆₀Cl₈, C₆₀Cl₁₀, C₆₀Cl₁₂, C₆₀Cl₁₄, and C₆₀Cl₂₆ were synthesized and characterized by chemical analysis, FTIR, ¹³C NMR, and MALDI TOF mass spectrometry. The experimental data supported the coexistence of several isomers of C₆₀Cl_n (n = 8, 10, 12, 14, 26); the mixtures were not separated so far. Semiempirical calculations (AM1, PM3) were used to analyze the addition patterns and resulted in the most favorable structures of C₆₀Cl_8-26. Chlorination of C₇₀ under various conditions invariably yielded C₇₀Cl₁₀.     

GENERATION OF HIGHER FULLERENES FROM LASER ABLATION OF CARBYNE AND C60 PHOTOPOLYMER ASTROCHEMICAL IMPLICATIONS

Laser ablation of targets of carbonaceous matter containing carbyne nanodomains (the sp hybridised carbon chains) or targets of C₆₀ photopolymer produced carbon clusters which have been detected by FT-ICR (Fourier-Transform Ion Cyclotron Resonance) mass spectrometer. When the carbonaceous matter containing carbyne has been employed as laser target, no C₆₀ has been generated but only fullerene cages from C₇₄ up to C₁₂₄. Larger cages were also obtained but with odd number. Starting from C₆₀ photopolymer, laser ablation regenerates free C₆₀ and creates a sequence of C₆₀ superior homologues all possessing even number and each member of the series is separated from the preceding and the following member by the loss or by the addition respectively of a C₂ unit. Fullerenes up to C₁₆₂ have been recorded. The implications about the presence of free C₆₀ fullerene in the interstellar and circumstellar space, its formation from carbyne chains and its stability towards its photopolymerization tendency and its regeneration from the photopolymer together with its superior homologues have been discussed thoroughly in the present paper.     

Effect of Solvents and Supporting Electrolytes on the Electrochemical Properties of C70 and its Comparison with C60

Surrounding medium effect on the electrochemical properties of C₇₀ was studied in 9 single, 2 mixture solvents and 7 supporting electrolytes by cyclic. voltammetry in the temperature range between 260 and 288K. The obtained results were analyzed and compared with those of C₆₀. It was shown that, due to the different structure between C₇₀ and C₆₀, the degree of these medium effect on their reduction potential was different. The solvent effect on the reduction of C₇₀ was more significant than that of C₆₀; on the other hand, the solvophobic interaction between the larger cations of supporting electrolyte and C₇₀ anions was weaker than that between the same cations and C₆₀ anions. In addition, C₇₀ redox couple showed better reversibility when the supporting electrolyte contains larger cations. C₇₀ redox potentials were also measured as a function of temperature, and the entropy changes of C₇₀reduction were calculated.     

Natural Fullerenes-Will they Offer a Hint to the Selective Synthesis of Fullerenes?

In addition to the known laboratory methods of preparing fullerenes, which generally start from carbon vapor, studies of naturally occurring C₆₀/C₇₀ suggest a catalytic process of fullerene formation that proceeds in solid phase under mild condition. Recent observation of C₆₀/C₇₀ in Yunnan coal and Kalerian C-rich rock is reviewed in the light of the above perspective.     

Electronic structure and electrical transport characteristics of C60, 2C60 and 4C60 fullerene molecules

The extended H?ckel method and the Green s function method were used to calculate the electronic structure and electrical transport of Au electrode-C₆₀, 2C₆₀ or 4C₆₀ fullerene-Au electrode systems. Furthermore, their electronic structure and electrical transport characteristics were compared and analyzed. The results show that (i) owing to the contact with the Au electrodes, the C₆₀, 2C₆₀ and 4C₆₀ molecules change in their electronic structures significantly, and their energy gaps between LUMO and HOMO are narrow; (ii) the bonding between C₆₀, 2C₆₀ or 4C₆₀ fullerene and Au electrodes is partially covalent and partially electrovalent; and (iii) the conductance of the three fullerenes conforms to the order of C₆₀>2C₆₀>4C₆₀.     

Addition Reactions of Benzyne, Dienes, Dichlorocarbene, and Oxygen to C60

Benzyne was found to add to C₆₀ in good yield to give C₆₀(C₆H₄)_n (n=1-4). Typical Diels-Alder dienes were also found to add to C₆₀ under thermally mild conditions. Adducts of C₆₀ with 2,3-dimethylbutadiene, cyclopentadiene, hexa-chlorocyclopentadiene, 1,3-diphenylisobenzofuran, and anthracene were obtained. Further reactions of these products such as elimination and autooxidation reactions were investigated. Addition reaction of dichlorocarbene to C₆₀ gave C₆₁Cl₂. Oxidation of C₆₀ with m-chloroperbenzoic acid gave C₆₀O_n(n=1, 2). All of the products were isolated by means of HPLC and characterized by mass spectroscopy.     

The Solubility of C60 Fullerene in Long Chain Fatty Acids Esters

A series of fatty acid esters of glycerol as linseed, sunflower, soybean and olive oils have been tested as C₆₀ fullerene solvents together with a mixture of methyl ester fatty acids derived from brassica oilseeds and used as a biofuel known as “biodiesel.” All the oils evaluated are effective solvents of C₆₀. The solubility of C₆₀ in the selected vegetable oils has been determined spectrophotometrically. The C₆₀ solubility in vegetable oils may pave the way for easier application of C₆₀ fullerene in medicinal chemistry and in additive chemistry for varnishes and fuels. It has been found that C₆₀ is not only soluble in the fatty acid esters but is also reactive with them under mild conditions, giving addition products easily recognized by a characteristic absorption band at 435 nm. The addition reaction mechanism has been discussed.     

Synthesis and Spectral Characterization of Difunctional Fullerenes

The oxidation of C₆₀ with m-chloroperbenzoic acid gave C₆₀O₂ with a high positional selectivity, as the ¹³C NMR analysis suggested. Diadducts C₆₀CCI₂O, C₆₀CCl₂(anthracene), C₆₀CCl₂[(CH₂CH₂)₂N₂], and C₆₀CCI₂[Pt-(PPh₃)₂] were synthesized, isolated, and characterized by negative ion FAB mass spectroscopy.     

GROUP TRANSFER AND DIMERIZATION PROCESSES OF C60(CN)2 UNDER ATMOSPHERIC PRESSURE IONIZATION CONDITIONS

Neutral and anionic C₆₀(CN)₂ were investigated with electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) mass spectrometry. It was observed that its anions underwent cyano- group and oxygen transfer, and dimerization processes in ESI conditions to form C₆₀(CN)₃H^-, C₆₀(CN)₂(OH₂)^-, [C₆₀(CN)₃H]^-₂, [C₆₀(CN)₂(OH₂)]^-₂ and [(C₆₀)₂(CN)₂(OH)]^-. Meanwhile, neutral C₆₀(CN)₂, for which no signal was observed in ESIMS, showed a base peak corresponding to C₆₀(CN)₂Cl^- in APCIMS spectra with CHCl₃ used as solvent, while only a molecular ion peak corresponding to C₆₀(CN)^-₂ was observed for the toluene solution of neutral C₆₀(CN)₂ in the same conditions. Possible mechanisms for group transfer and dimerization were proposed based on these observations.     

Effect of Substituents on the Redox Potentials of C60 Derivatives

The electrochemical properties of four C₆₀ derivatives (compounds 1∼4) were investigated with cyclic voltammetry (CV), and compared with that of C₆₀. The reduction potentials of compound 1∼3 shifted to more negative positions than C₆₀, and their oxidation peaks appeared at the lower potentials. Significantly, the reduction potentials of compound 4 shifted to more positive positions than C₆₀, which is advantageous to form charge-transfer complexes with more donors. So the reduction properties in different solvents and in situ NIR absorption spectra of compound 4 were studied in more details. In addition, the AM1 molecular orbital calculation was performed on C₆₀ and compound 1∼4 for the explanation of the potential shifts. The reduction potentials of these compounds exhibited good linear relationships with the calculation LUMO or LUMO+1 energy levels.     

Charge Transfer in Fullerene-Conducting Polymer Compositex: Electronic and Excitonic Properties

C₆₀ doping into conducting polymer with highly extended π-electron system in the main chain induces remarkable quenching of photoluminescence in conducting polymer and drastic enhancement of photoconductivity. These results can be explained in terms of photo-induced charge transfer between conducting polymer and C₆₀. That is, photoexcited excitons or exciton-polarons on conducting polymer are effectively dissociated at C₆₀ molecules transferring electrons to C₆₀. Photoexcitation of C₆₀ results in the transfer of hole from C₆₀ to conducting polymer. These novel C₆₀ doping effects have been observed not only in conducting polymers with non-degenerated ground state structures but also those with degenerated ground state structure such as di-substituted acetylene polymers with solitonic electronic systems.

Highly effective photo-induced charge transfer has been also observed in conducting polymer/C₆₀ heterojunctions, which are interpreted as donor (D)-acceptor (A) photocell. Based on this finding we have demonstrated an organic photovoltaic cell with D-A double heterojunction, Al/C₆₀/OEP/conducting polymer/TTO, in which OEP is octaethylporphine as an light absorbing antenna molecule. Novel characteristics have also been observed in various other junction devices utilizing C₆₀ doped conducting polymer.

Granular and multiphase superconductivity has been found in C₆₀-conducting polymer-alkali metal composites.

Effect of other type of fullerenes such as C₇₀, modified C₆₀ and C₆₀ polymers, and also effect of C₆₀ doping in polysilanes and their derivatives have also been studied.     

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.     

Investigations of the Interaction of Nickel and Carbon Monoxide with Solid Films of C60 and C70 by UV and X-Ray Photoelectron Spectroscopy

Based on UV and X-ray photoelectron spectroscopy, it is shown that nickel metal clusters deposited on solid C₆₀ and C₇₀ films cause marked changes in the valence band spectra. In addition, the C 1s core-level of the fullerenes shift to lower binding energies while the Ni 2p_3/2 core level shifts towards higher binding energies, especially at small metal coverages. These observations signify the occurrence of charge-transfer from the nickel metal to the fullerene. We also show that CO adsorbs weakly on C₆₀ and C₇₀ surfaces.     

Synthesis of Radiolabeled Fullerenes C60 and C70

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.     

Bromination of [60]Fullerene. II. Crystal and Molecular Structure of [60]Fullerene Bromides, C60Br6, C60Br8, and C60Br24

The crystal and molecular structures of the bromofullerene solvates C₆₀Br₆·0.5C₆H₅Cl·0.5Br₂, C₆₀Br₈·1.5(o-C₆H₄Cl₂), C₆₀Br₈·Br₂, C₆₀Br₈·0.5C₆H₅Br·0.5Br₂, and C₆₀Br₂₄·2Br₂ have been determined by single crystal X-ray diffraction. The molecular species C₆₀Br₆, C₆₀Br₈, and C₆₀Br₂₄ which have idealized C_s, C_2v , and T_h symmetries, respectively, have several different types of C-Br and C-C bonds. A comparison between different solvates of the same bromofullerenes revealed a larger stability of the packing modes for the C₆₀Br₆ and C₆₀Br₂₄ solvates, whereas the C₆₀Br₈ solvates showed different packing motifs dependent on the nature and amount of the solvent molecules.     

Study of the Submerged Electric Arc in Hexane in Presence of C60 Fullerene

The effect of the electric arc between graphite electrodes submerged in n-hexane solutions of C₆₀ fullerene has been studied by electronic absorption spectroscopy, liquid chromatographic analysis (HPLC-DAD), and FT-IR spectroscopy. The experimental results show that C₆₀ does not appear able to inhibit the polyynes' formation at the concentration used. Polyynes are formed in large amounts as usual from the graphite arc, and polycyclic aromatic hydrocarbons have been detected as by-products. Prolonged arcing causes the disappearance of C₆₀ from the solution. There is experimental evidence that C₆₀ undergoes radical addition reactions during the early stages of arcing.     

Bromination of [60]Fullerene. I. High-Yield Synthesis of C60Brx (x=6, 8, 24)

The systematic study of the bromination of C₆₀ was performed under various experimental conditions. Application of some chloroarenes as reaction media resulted in the high-yield (70-96%) selective synthesis of C₆₀Br₆ and C₆₀Br₈. Direct bromination of fullerene yielded either C₆₀Br₈, C₆₀Br₁₄, or C₆₀Br₂₄ depending on the reaction time. Possible pathways of bromination of C₆₀Br₈ were analyzed using semiempirical (AM1) calculations, two most probable molecular structures are conjectured for the first isolated C₆₀Br₁₄.     

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

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.