Isolation and Crystallographic Characterization of the Labile Isomer of Y@C82 Cocrystallized with Ni(OEP): Unprecedented Dimerization of Pristine Metallofullerenes.
Although the major isomers of M@C82 (namely M@C2v (9)-C82 , where M is a trivalent rare-earth metal) have been intensively investigated, the lability of the minor isomers has meant that they have been little studied. Herein, the first isolation and crystallographic characterization of the minor Y@C82 isomer, unambiguously assigned as Y@Cs (6)-C82 by cocrystallization with Ni(octaethylporphyrin), is reported. Unexpectedly, a regioselective dimerization is observed in the crystalline state of Y@Cs (6)-C82 . In sharp contrast, no dimerization occurs for the major isomer Y@C2v (9)-C82 under the same conditions, indicating a cage-symmetry-induced dimerization process. Further experimental and theoretical results disclose that the regioselective dimer formation is a consequence of the localization of high spin density on a special cage-carbon atom of Y@Cs (6)-C82 which is caused by the steady displacement of the Y atom inside the Cs (6)-C82 cage.
State Key Laboratory of Materials Processing and Die & Mold Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, 1037, Luoyu Road, Wuhan, 430074, P.R. China.
Lipiao
L
Bao
State Key Laboratory of Materials Processing and Die & Mold Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, 1037, Luoyu Road, Wuhan, 430074, P.R. China.
Changwang
C
Pan
Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba, Tsukuba, Ibaraki, 305-8577, Japan.
Zdenek
Z
Slanina
Department of Physical and Macromolecular Chemistry, Charles University in Prague, 12843, Prague 2, Czech Republic.
Filip
F
Uhlik
State Key Laboratory of Materials Processing and Die & Mold Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, 1037, Luoyu Road, Wuhan, 430074, P.R. China.
Takeshi
T
Akasaka
State Key Laboratory of Materials Processing and Die & Mold Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, 1037, Luoyu Road, Wuhan, 430074, P.R. China. lux@hust.edu.cn.
Xing
0000-0003-2741-8733
X
Lu
density functional calculations; dimerization; metallofullerenes; structure elucidation; yttrium