title: Stabilization of a Chlorinated (#4348)C66:C2v Cage by Encapsulating Monometal Species: Coordination between Metal and Double Hexagon-Condensed Pentalenes.
abstract: Carbon cages in endohedral and exohedral fullerene derivatives are usually different. A recent report suggested that chlorofullerene C66Cl10:Cs and endohedral metallofullerene (EMF) Sc2@C66 shared the same cage (#4348)C66:C2v, while it was denied by the definitive characterization of Sc2@C66, which actually possesses the (#4059)C66:C2v isomer. Here, we show that a (#4348)C66:C2v 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, (#4348)C66:C2v-based mono-EMFs M@C2v(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 (#4169)C66:Cs, 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@C2v(4348)-C66 over M@Cs(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@C2v(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.
authors.affiliation: Institute for Chemical Physics and Department of Chemistry, School of Science, State Key Laboratory of Electrical Insulation and Power Equipment, Xi'an Jiaotong University , Xi'an 710049, China.
authors.forename: Qiao-Zhi
authors.initials: QZ
authors.lastname: Li
authors.affiliation: Institute for Chemical Physics and Department of Chemistry, School of Science, State Key Laboratory of Electrical Insulation and Power Equipment, Xi'an Jiaotong University , Xi'an 710049, China.|Fukui Institute for Fundamental Chemistry, Kyoto University , Kyoto 606-8103, Japan.
authors.forename: Jia-Jia
authors.initials: JJ
authors.lastname: Zheng
authors.affiliation: Institute for Chemical Physics and Department of Chemistry, School of Science, State Key Laboratory of Electrical Insulation and Power Equipment, Xi'an Jiaotong University , Xi'an 710049, China.
authors.forename: Ling
authors.initials: L
authors.lastname: He
authors.affiliation: Fukui Institute for Fundamental Chemistry, Kyoto University , Kyoto 606-8103, Japan.
authors.forename: Shigeru
authors.initials: S
authors.lastname: Nagase
authors.affiliation: Institute for Chemical Physics and Department of Chemistry, School of Science, State Key Laboratory of Electrical Insulation and Power Equipment, Xi'an Jiaotong University , Xi'an 710049, China.
authors.forename: Xiang
authors.initials: X
authors.lastname: Zhao