Zur Bildung von Fullerenen und endohedralen Metallofullerenen: Darstellung im Hochfrequenzofen

Formation of Fullerenes and Endohedral Metallofullerenes: Preparation in a Radiofrequency Furnace A thermodynamic analysis of the reaction of formation is presented for C₆₀. The alternative route for the preparation of fullerenes by evaporating carbon in a RF-furnace is described. This process is characterized by its broad variability and by comparatively mild conditions which, in addition, may be measured and controlled rather precisely. Thus, it offers favorite facilities for the production of soots with high contents of fullerenes and endohedral fullerenes. So far, LaC₈₂ could be extracted using toluene.     

C60F14OFPh3, a fluoroxy derivative of C60F15Ph3; evidence for the presence of ‘missing’ fluorine through restricted rotation of a phenyl group

From the reaction of C₆₀F₁₈ with benzene in the presence of SbCl₅ we have isolated a compound of 1252 amu indicated to be C₆₀F₁₄OFPh₃, a fluoroxyfullerene. Temperature-variable ¹H NMR shows that one phenyl group suffers restricted rotation on cooling to 218 K, attributed to the presence of the OF group which, as in the case of the recently characterised C₆₀F₁₇OF, fails to give a signal for this group in the ¹⁹F NMR. We have isolated also, C₆₀F₁₄O₂FPh₃ (1268 amu) a mixture of oxahomo derivatives of C₆₀F₁₄OFPh₃ arising from oxygen insertion into FCCF bonds. Theoretical calculations for C₆₀F₁₄OFPh₃ indicate that the phenyl group nearest to the OF group is twisted out of the plane containing the other two.     

含铥金属富勒烯的生成及其特殊的溶解行为

金属富勒烯的合成及结构研究是当前富勒烯化学研究的重要内容[1]．一些稀土金属元素，如Sc[2]、Y[3]及大部分斓系元素（La、Ce、Nd、Sin、Eu、Gd、Tb、Ho）[4]形成的金属富勒烯已被合成出来．但仍有一些稀土富勒烯的合成尚未见报道，使人们难以对金属富勒烯的形成机制及物化性能作出全面的判断．本文采用原位活化、交换电极回放电弧放电及两步提取法首次得到含锡金属富勒烯．通过空白对比实验确定了Tin＠C。怕9生成．对甲苯及毗院提取液的质谱研究表明含镀金属富勒烯具有区别于其它金属富勒烯的特殊的溶解性能，显示出其可能具有独特的…     

The support and characterization of C60 and MoO3 on Al2O3

A new type of catalyst from supporting C₆₀ on MoO₃ and Al₂O₃ has been prepared. The effect of different order of impregnation and calcination atmosphere on catalyst are investigated by the solution test in toluene, UV-VIS spectroscopy and temperature programmed reduction (TPR). The results show that when the catalyst was prepared by supporting MoO₃ on C₆₀/Al₂O₃ and calcined in N₂, there is a stronger interaction between C₆₀, MoO₃ and Al₂O₃, but when supporting C₆₀ on MoO₃/Al₂O₃, the interaction is relatively weak. We consider that in the former method a new complex, Mo–C₆₀–O–Al, is formed.     

A Mathematical Model of the Carbon Arc Reactor for Fullerene Synthesis

A mathematical model of the carbon arc process for the synthesis of fullerenes (C ₆₀ , C ₇₀ ) is developed. The two-dimensional model solves for the velocities, temperature, and total concentration of carbon species. The net emission coefficient method is used for the radiation term. The carbon species conservation equations consider the evaporation of carbon from the anode, cathode surface deposition, and carbon condensation. The thermodynamic and transport properties are calculated as a function of temperature and carbon mass fraction, using the method of Chapman–Enskog. Erosion rates used by the model are determined experimentally. Calculated fields of the velocities, temperatures, carbon mass fraction and current intensity are presented. Comparison is made of the behavior of the arc at 1 and 4 mm interelectrode gaps, and between operation in argon and in helium. The results of simulations provide a justification for the higher yields observed in helium compared to the argon case.     

富勒烯碳-60,碳-70的电化学研究进展

短短的几年,随着各种物理与化学研究方法的相继介入,以C_(60)和C_(70)为代表的富勒烯研究取得了令人瞩目的成就。跟踪最新进展,引文41篇,本文就其电化学方面的研究工作做了系统的综述。     

Sulfur-containing dihydro-pyrrolo [60]fullerene derivatives via 1,3-dipolar cycloadditions of glycine imine esters to C60

C₆₀ reacts thermally with 1,3-dipoles, formed in situ, from sulfide-bearing imines of glycine esters, and affords dihydro-pyrrolo [60]fullerene derivatives containing a vinylic sulfide group, which were isolated in good yields, and characterized with ¹H and ¹³C NMR, FTIR, UV-vis spectroscopies, and with FAB, ESI mass spectrometries. The new derivatives contain a sulfide, an imine, and an ester functionality for further chemical transformations. Mechanistic considerations with regard to the loss of a mercaptan molecule in the course of the cycloaddition are deployed.     

C60 and carbon: a postbuckminsterfullerene perspective

The discovery of the fullerenes and nanotubes has completely changed our perspective on various aspects of carbon chemistry and materials science in quite fundamental ways. The experiments, which uncovered C₆₀, occurred between 1985 and 1990 and there are lessons to be learned of various kinds over the way scientific advances occur and more importantly the way misconceptions can propagate. For instance much of our received wisdom over the behaviour of carbon, in particular graphite on a microscopic scale, was really quite ill-conceived and certainly misleading. Questions might be asked as to why it took almost till the end of the 20th century for the fact to be uncovered that the elegant C₆₀ molecule had been lurking in the dark shadows of soot chemistry all the time. After all, mass spectrometric techniques were sufficiently advanced for the discovery to have been made in the 1960’s—perhaps even earlier. Some of these issues are addressed here and the discussion gives an insight into the curiously unpredictable way fundamental scientific advances sometimes occur and also highlights the limitations of applied research in this case.     

Structural and electronic properties of supramolecular C60:RU(II)(bipy)3:C60 triad: Ab initio van der Waals calculations

We have investigated the influence of non-local dispersion interactions and temperature on the structure and electronic properties of Ru(bipy)₃-(C₆₀)₂ triad using the ab initio van der Waals density functional (vdW-DF) calculations. It was found that non-local dispersion interactions affects slightly on the structural geometry and charge transfer property of the system under study. Therefore, it's not necessary to consider dispersion interactions which are computationally more expensive than the conventional DFT calculations for the presented supramolecules.The obtained results from the ab initio MD simulations indicated that structural property of respected molecule varies at various temperatures. The Mulliken charge analyses show a remarkable charge transfer about 0.64 electrons between Ru (bipy)₃-bridges as donors and fullerenes as acceptors entities in the isolated molecule by increasing the temperature, the charge transfer was also increased.Our first-principles results for the isolated complex showed that the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) states were located on the fullerene spheroid and thus the charge separation (orbital localization) is not desirable. However, increasing of temperature causes the LUMO's to localize on the acceptor moieties (fullerenes) and the HOMO's on the donor moieties (Ru(bipy)₃). From the results obtained for the molecular orbitals we found that the best distribution is occurred at ambient condition (300 K).