X-ray Structures of Sc2C2@C2n (n = 40鈥?2): In-Depth Understanding of the Core鈥揝hell Interplay in Carbide Cluster Metallofullerenes

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• 作者：Hiroki Kurihara ; Xing Lu ; Yuko Iiduka ; Hidefumi Nikawa ; Makoto Hachiya ; Naomi Mizorogi ; Zdenek Slanina ; Takahiro Tsuchiya ; Shigeru Nagase ; Takeshi Akasaka
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：January 2, 2012
• 年：2012
• 卷：51
• 期：1
• 页码：746-750
• 全文大小：269K
• 年卷期：v.51,no.1(January 2, 2012)
• ISSN：1520-510X

文摘

X-ray analyses of the cocrystals of a series of carbide cluster metallofullerenes Sc₂C₂@C_2n (n = 40鈥?2) with cobalt(II) octaethylporphyrin present new insights into the molecular structures and cluster鈥揷age interactions of these less-explored species. Along with the unambiguous identification of the cage structures for the three isomers of Sc₂C₂@C_2v(5)-C₈₀, Sc₂C₂@C_3v(8)-C₈₂, and Sc₂C₂@D_2d(23)-C₈₄, a clear correlation between the cluster strain and cage size is observed in this series: Sc鈥揝c distances and dihedral angles of the bent cluster increase along with cage expansion, indicating that the bending strain within the cluster makes it pursue a planar structure to the greatest degree possible. However, the C鈥揅 distances within Sc₂C₂ remain unchanged when the cage expands, perhaps because of the unusual bent structure of the cluster, preventing contact between the cage and the C₂ unit. Moreover, analyses revealed that larger cages provide more space for the cluster to rotate. The preferential formation of cluster endohedral metallofullerenes for scandium might be associated with its small ionic radius and the strong coordination ability as well.