冯莱课题组在Chem. Eur. J. 上发表论文
标题：Mapping the Metal Positions inside Spherical C80 Cages: Crystallographic and Theoretical Studies of Ce2@D5h-C80 and Ce2@h-C80

作者：Lai Feng,*Mitsuaki Suzuki,Naomi Mizorogi,Xing Lu,Michio Yamada,Takeshi Akasaka,*and Shigeru Nagase*

摘要：The dynamic positions of the dimetallic cluster inside the mid-sized spherical cages of C80–C82 have been seldom studied, despite the high abun-dance of M2@C2n(2 n = 80, 82) species among various endohedral metalloful lerenes. Herein, using crystallographic methods, we first unambiguously map the metal positions for both Ce2@D 5h-C80 and Ce2@Ih-C80, showing how the symmetry or geometrical change in cage structure can influence the mo-tional behavior of the cluster. Inside the D5 h
cage, the primary cerium sites have been identified along a cage belt of the contiguous hexagons, which suggests the significant influence of such a cage motif on endohedral cluster motion. Further analysis revealed a dis-torted D5h cage owing to the “punch-out” effect of cerium atoms. The conse quence is the presence of two localized electrostatic potential minima inside the cage of ( D5 h-C80)6, thus reflecting
the primary ionic cerium–cage interac-tion. In contrast, a different motional behavior of Ce2 cluster was observed inside the Ih cage. With the major cerium sites, the molecule of Ce2@ Ih-C80 presented an approximate D 2h con-figuration. With the combined theoreti-cal study, we propose that the addition-al unidentified influence of NiII(OEP)
(OEP = octaethylporphyrin) might be also relevant for the location of cerium sites inside the Ih cage.

Chem. Eur. J. 2013, 19, 988 – 993