Influence of the cage size on the dynamic behavior of fullerenes: a study of (13)c NMR spin-lattice relaxation

Abstract

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.