Stabilization of a Chlorinated #4348C66:C2v Cage by Encapsulating Monometal Species: Coordination between Metal and Double Hexagon-Condensed Pentalenes

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• 作者：Qiao-Zhi Li ; Jia-Jia Zheng ; Ling He ; Shigeru Nagase ; Xiang Zhao
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：August 1, 2016
• 年：2016
• 卷：55
• 期：15
• 页码：7667-7675
• 全文大小：546K
• 年卷期：0
• ISSN：1520-510X

文摘

Carbon cages in endohedral and exohedral fullerene derivatives are usually different. A recent report suggested that chlorofullerene C₆₆Cl₁₀:C_s and endohedral metallofullerene (EMF) Sc₂@C₆₆ shared the same cage ^#4348C₆₆:C_2v, while it was denied by the definitive characterization of Sc₂@C₆₆, which actually possesses the ^#4059C₆₆:C_2v isomer. Here, we show that a ^#4348C₆₆:C_2v cage with a double hexagon-condensed pentalene (DHCP) moiety, which was captured by exohedral chlorination, is also capable of being stabilized by encapsulating tri- or divalent monometal (M) species. On the basis of density functional theory calculations combined with statistical mechanics analyses, ^#4348C₆₆:C_2v-based mono-EMFs M@C_2v(4348)-C₆₆ (M = Tb, La, Y, and Yb) were demonstrated to be the most stable and predominant isomers at the fullerene formation temperature region, while another chlorinated cage ^#4169C₆₆:C_s, featured with triple sequentially fused pentagon (TSFP) moiety, is less favorable to be obtained in the form of EMFs, although these two cages can be interconverted by a simple Stone–Wales transformation. The superiority of M@C_2v(4348)-C₆₆ over M@C_s(4169)-C₆₆ comes from the stronger interaction of M–DHCP over that of M–TSFP in both ionic and covalent bonding aspects. In addition, size-selective complexation of host [n]cycloparaphenylene ([n]CPP) and Tb@C_2v(4348)-C₆₆ was simulated, showing that [10]CPP exhibits the best affinity toward Tb@C₆₆, which provides a new opportunity for isolation and characterization of C₆₆-based mono-EMFs.