M@C78 (M = U, Th): Inherent Topological Connectivity Existed in Thermodynamically Stable Isomers and the Possibility of an Endohedral Fullerene Containing One Heptagon Ring.

The density functional theory combined with statistical thermodynamic analyses of M@C78 (M = U and Th) demonstrated that four isomers, M@D3h(24109)-C78, M@C2v(24107)-C78, M@C1(22595)-C78, and M@C1(23349)-C78, and a nonclassical isomer, M@C1(id7)-C78, containing one heptagon ring possess outstanding thermodynamic stabilities in the two M@C78 series. Especially, the M@C1(id7)-C78 isomer is the first nonclassical C78 fullerene that can exist stably. Importantly, these five fullerene cages are found to be related in the form of Stone-Wales (SW) transformations. Geometric analyses disclosed that, unlike lanthanide metals, actinide metals are more likely to bond with sumanene-type hexagonal rings when they are encapsulated in IPR C78 cages. Frontier molecular orbital analysis showed that both U and Th atoms donate four electrons to the C78 carbon cages.

[1]  Xiang Zhao,et al.  Theoretical Insight into Actinide Monometallofullerene Th@C74 with Four-Electron-Transfer Characteristics , 2021 .

[2]  Xiang Zhao,et al.  Encapsulation of Monometal Uranium into Fullerenes C2n (2n = 70-74): Important Ionic U4+C2n4- Characters and Covalent U-Cage Bonding Interactions. , 2019, Inorganic chemistry.

[3]  Xing Lu,et al.  Eu@C72: Computed Comparable Populations of Two Non-IPR Isomers , 2017, Molecules.

[4]  P. Bouř,et al.  Properties of the Only Thorium Fullerene, Th@C84, Uncovered. , 2017, The journal of physical chemistry. A.

[5]  A. Rodríguez‐Fortea,et al.  Unique Four-Electron Metal-to-Cage Charge Transfer of Th to a C82 Fullerene Cage: Complete Structural Characterization of Th@C3v(8)-C82. , 2017, Journal of the American Chemical Society.

[6]  Luis Echegoyen,et al.  Zigzag Sc2C2 Carbide Cluster inside a [88]Fullerene Cage with One Heptagon, Sc2C2@Cs(hept)-C88: A Kinetically Trapped Fullerene Formed by C2 Insertion? , 2016, Journal of the American Chemical Society.

[7]  Yi-Jun Guo,et al.  Single Step Stone-Wales Transformation Linking Two Thermodynamically Stable Sc2O@C78 Isomers. , 2016, Inorganic chemistry.

[8]  Tao Wei,et al.  Chlorination-Promoted Skeletal-Cage Transformations of C88 Fullerene by C2 Losses and a C-C Bond Rotation. , 2015, Chemistry.

[9]  Tao Wei,et al.  Two successive C2 losses from C86 fullerene upon chlorination with the formation of non-classical C84Cl30 and C82Cl30. , 2015, Chemistry, an Asian journal.

[10]  S. Nagase,et al.  Quantum-chemical calculations of the metallofullerene yields in the X@C74, L@C74, and Z@C82 series , 2015 .

[11]  S. Nagase,et al.  Quantum chemical determination of novel C82 monometallofullerenes involving a heterogeneous group. , 2014, Inorganic chemistry.

[12]  Kamran B. Ghiassi,et al.  Synthesis and structure of LaSc2N@C(s)(hept)-C80 with one heptagon and thirteen pentagons. , 2014, Angewandte Chemie.

[13]  Shangfeng Yang,et al.  Chlorination of IPR C100 fullerene affords unconventional C96 Cl20 with a nonclassical cage containing three heptagons. , 2014, Angewandte Chemie.

[14]  Tao Wei,et al.  Cage shrinkage of fullerene via a C2 loss: from IPR C90(28)Cl24 to nonclassical, heptagon-containing C88Cl22/24. , 2013, Inorganic chemistry.

[15]  Jinying Zhang,et al.  Missing small-bandgap metallofullerenes: their isolation and electronic properties. , 2013, Angewandte Chemie.

[16]  Tao Yang,et al.  Missing metallofullerene Yb@C72: A density functional theory survey , 2013 .

[17]  S. Nagase,et al.  Structural Determination on Yb@C78 Reveals an Unexpected Relationship of Yb@C2n (2n = 74–80) , 2012 .

[18]  Tian Lu,et al.  Multiwfn: A multifunctional wavefunction analyzer , 2012, J. Comput. Chem..

[19]  Eiji Osawa,et al.  Can a metal-metal bond hop in the fullerene cage? , 2011, Chemistry.

[20]  Xing Lu,et al.  Radical derivatives of insoluble La@C74: X-ray structures, metal positions, and isomerization. , 2011, Angewandte Chemie.

[21]  Chuanbao Chen,et al.  Chlorination of C86 to C84Cl32 with nonclassical heptagon-containing fullerene cage formed by cage shrinkage. , 2010, Angewandte Chemie.

[22]  Matthias Krause,et al.  C78 cage isomerism defined by trimetallic nitride cluster size: a computational and vibrational spectroscopic study. , 2007, The journal of physical chemistry. B.

[23]  Filip Uhlík,et al.  Computing relative stabilities of metallofullerenes by Gibbs energy treatments , 2007 .

[24]  M. Jansen,et al.  Synthesis, isolation and characterization of new endohedral fullerenes M@C72 (M = Eu, Sr, Yb) , 2006 .

[25]  Roger Taylor,et al.  Isolation of Two Seven-Membered Ring C58 Fullerene Derivatives: C58F17CF3 and C58F18 , 2005, Science.

[26]  Y. Achiba,et al.  13C NMR study of Ca@C74: the cage structure and the site-hopping motion of a Ca atom inside the cage , 2004 .

[27]  M. Jansen,et al.  The structure of Ba@C74. , 2004, Journal of the American Chemical Society.

[28]  Z. Gu,et al.  Synthesis, Isolation, and Spectroscopic Characterization of Ytterbium-Containing Metallofullerenes , 2004 .

[29]  M. Dolg,et al.  Segmented contraction scheme for small-core lanthanide pseudopotential basis sets , 2002 .

[30]  H. Stoll,et al.  Valence basis sets for relativistic energy-consistent small-core actinide pseudopotentials , 2001 .

[31]  Charles L. Wilkins,et al.  C62, a Non-Classical Fullerene Incorporating a Four-Membered Ring , 2000 .

[32]  O. Boltalina,et al.  Electron Affinity of Some Endohedral Lanthanide Fullerenes , 1997 .

[33]  Patrick W. Fowler,et al.  C62: Theoretical Evidence for a Nonclassical Fullerene with a Heptagonal Ring , 1996 .

[34]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[35]  R. Whetten,et al.  Fullerene Isomerism: Isolation of C2v,-C78 and D3-C78 , 1991, Science.

[36]  F. Wudl,et al.  The Higher Fullerenes: Isolation and Characterization of C76, C84, C90, C94, and C70O, an Oxide of D5h-C70 , 1991, Science.

[37]  H. W. Kroto,et al.  The stability of the fullerenes Cn, with n = 24, 28, 32, 36, 50, 60 and 70 , 1987, Nature.

[38]  S. C. O'brien,et al.  C60: Buckminsterfullerene , 1985, Nature.

[39]  Eamonn F. Healy,et al.  Development and use of quantum mechanical molecular models. 76. AM1: a new general purpose quantum mechanical molecular model , 1985 .

[40]  E. Ōsawa,et al.  Combined topological and energy analysis of the annealing process in fullerene formation. Stone–Wales interconversion pathways among IPR isomers of higher fullerenes , 1998 .