화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.128, No.27, 8884-8889, 2006
Preparation and structure of CeSc2N@C80: An icosahedral carbon cage enclosing an acentric CeSc2N unit with buried f electron spin
Herein, we report the preparation, purification, and characterization of a mixed trimetallic nitride endohedral metallofullerene, CeSc2N@C-80. Single-crystal X-ray diffraction shows that CeSc2N@C80 consists of a four-atom asymmetric top (CeSc2N) inside a C-80 (I-h) carbon cage. Unlike the situation in most endohedrals of the M3N@C-2n type, the nitride ion is not located at the center of the carbon cage but is offset by 0.36 angstrom in order to accommodate the large Ce-III ion. The cage carbon atoms near the endohedral Ce and Sc atoms exhibit significantly larger pyramidal angles than the other carbon atoms on the C80 cage. Surprisingly, at ambient temperature, the C-13 NMR spectrum exhibits isotropic motional averaging yielding only two signals (3 to 1 intensity ratio) for the icosahedral C80 cage carbons. At the same temperature, the Sc-45 NMR exhibits a relatively narrow, symmetric signal (2700 Hz) with a small temperature dependent Curie shift. A rotation energy barrier (E-a = 79 meV) was derived from the Sc-45 NMR line-width analysis. Finally, the XPS spectrum for CeSc2N@C-80 confirms a + 3 oxidation state for cerium, Ce3+-4f(1)5d(0)). This oxidation state and the Curie shift are consistent with a weakly paramagnetic system with a single buried f electron spin.