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A detailed study on the relaxation mechanisms of higher cage fullerene sizes is done as a prerequisite for studies of the influence of the endohedral structures on fullerene cage carbon relaxation. Recent studies of the dynamic behavior of C(60) and C(70) in aromatic solvents and CS(2) solution show the influence of the shape and the symmetry of the cage to be highly important as well as the influence of the solvent to be negligible. As higher fullerene cages have more than one stable isomer, the isolation of isomeric pure structures is of high importance for a detailed study of the dynamic behavior of such fullerenes. Here we investigated the three higher fullerene cage isomers D(2)-C(76), C(2v)(3)-C(78), and D(2)-C(80) with respect to the relaxation rate of the carbons measured in their temperature dependence. Thus, we study the influence on the relaxation of the carbons and the dynamic behavior of these fullerenes in solution. Besides the diffusion dependence on the shape of the carbon cage, the relaxation behavior at lower temperatures is found to be dependent on the difference in chemical shift anisotropy within the carbon cage. This difference is originated from the changes of symmetry and results in polarization of electron density. Furthermore, the mobility of the carbons is influenced by their pyramidalization.

The world of endohedral fullerenes was significantly enlarged over the past seven years by the cluster fullerenes, which contain structures such as the M(2)C(2) carbides and the M(3)N nitrides. While the carbide clusters are generated under the standard arc-burning conditions according to stabilization conditions, the nitride cluster fullerenes (NCFs) are formed by varying the composition of the cooling gas atmosphere in the arc-burning process. The special conditions for NCF synthesis is described in detail and the optimum conditions for the production of NCFs as the main product in fullerene syntheses are given. A general review of all NCFs reported to date consists of the structures, properties, and stability of the NCFs as well as the abundance of the NCFs in the fullerene soot. It is shown that all cages with even carbon atoms from C(68) to C(98) are available as endohedral nitride cluster structures (with the exception of C(72), C(74), and C(76)). Specifically, the NCFs form the largest number of structures that violate the isolated pentagon rule (IPR). Finally some practical applications of these cluster fullerenes are illustrated and an outlook is given, taking the superior stability of these endohedral fullerenes into account.

Electrochemical reduction of ordered C60 fullerene films in aqueous solution was studied by AFM, FTIR and Raman spectroscopy, mass spectrometry and elastic recoil detection analysis. During the irreversible reduction process the film morphology changed from a heteroepitaxial (111) surface to a nanostructured array with clusters of 20 to 50 nm lateral size on average. On the molecular level the initial C60 underwent electrochemical reactions to form C60 polymers and hydrogenated C60. Chemical follow-up reactions of electrochemically formed C60- with water are responsible for the different reduction behaviour of C60 films in aqueous solution compared to C60 reduction in organic solvents and to C60 doping with alkali metals. Based on the spectroscopic analysis a reaction scheme accounting for the chemical processes at the C60 / aqueous electrolyte interface is presented.

Electrochemical nanostructuring of ordered C60 fullerene layers in aqueous solution was studied by in situ Raman spectroelectrochemistry. A completely changed molecular film structure was found for nanostructured films. C60 polymers/oligomers and hydrogenated C60 were identified as the main fullerene structures after nanostructuring. No significant contributions of Ax C60 fullerides (A=alkaline metal; x=1, 3, 6) were found. [ABSTRACT FROM AUTHOR]