화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.133, No.42, 16911-16919, 2011
Large Endohedral Fullerenes Containing Two Metal Ions, Sm-2@D-2(35)-C-88, Sm-2@C-1(21)-C-90, and Sm-2@D-3(85)-C-92, and Their Relationship to Endohedral Fullerenes Containing Two Gadolinium Ions
The carbon soot obtained by electric arc vaporization of carbon rods doped with Sm2O3 contains a series of monometallic endohedral fullerenes, Sm@C-2n, along with smaller quantities of the dimetallic endohedrals Sm-2@C-2n with n = 44, 45, 46, and the previously described Sm-2@D-3d(822)-C-104. The compounds Sm-2@C-2n with n = 44, 45, 46 were purified by high pressure liquid chromatography on several different columns. For endohedral fullerenes that contain two metal atoms, there are two structural possibilities: a normal dimetallofullerene, M-2@C-2n, or a metal carbide, M-2(mu-C-2)@C2n-2. For structural analysis, the individual Sm-2@C-2n endohedral fullerenes were cocrystallized with Ni-(octaethylporphyrin), and the products were examined by single-crystal X-ray diffraction. These data identified the three new endohedrals as normal dimetallofullerenes and not as carbides: Sm-2@D-2(35)-C-88, Sm-2@C-1(21)-C-90, and Sm-2@D-3(85)-C-92. All four of the known Sm-2@C-2n endohedral fullerenes have cages that obey the isolated pentagon rule (IPR). As the cage size expands in this series, so do the distances between the variously disordered samarium atoms. Since the UV/vis/NIR spectra of Sm-2@D-2(35)-C-88 and Sm-2@C-1(21)-C-90 are very similar to those of Gd2C90 and Gd2C92, we conclude that Gd2C90 and Gd2C92 are the carbides Gd-2(mu-C-2)@D-2(35)-C-88 and Gd-2(mu-C-2)@C-1(21)-C-90, respectively.