title: Isomeric Sc2O@C78Related by a Single-Step Stone-Wales Transformation: Key Links in an Unprecedented Fullerene Formation Pathway.
abstract: It has been proposed that the fullerene formation mechanism involves either a top-down or bottom-up pathway. Despite different starting points, both mechanisms approve that particular fullerenes or metallofullerenes are formed through a consecutive stepwise process involving Stone-Wales transformations (SWTs) and C2losses or additions. However, the formation pathway has seldomly been defined at the atomic level due to the missing-link fullerenes. Herein, we present the isolation and crystallographic characterization of two isomeric clusterfullerenes Sc2O@C2v(3)-C78and Sc2O@D3h(5)-C78, which are closely related via a single-step Stone-Wales (SW) transformation. More importantly, these novel Sc2O@C78isomers represent the key links in a well-defined formation pathway for the majority of solvent-extractable clusterfullerenes Sc2O@C2n(n = 38-41), providing molecular structural evidence for the less confirmed fullerene formation mechanism. Furthermore, DFT calculations reveal a SWT with a notably low activation barrier for these Sc2O@C78isomers, which may rationalize the established fullerene formation pathway. Additional characterizations demonstrate that these Sc2O@C78isomers feature different energy bandgaps and electrochemical behaviors, indicating the impact of SW defects on the energetic and electrochemical characteristics of metallofullerenes.
authors.affiliation: College of Physics, Optoelectronics and Energy & Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University , Suzhou 215006, China.
authors.forename: Yajuan
authors.initials: Y
authors.lastname: Hao
authors.affiliation: College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou 215163, China.
authors.forename: Qiangqiang
authors.initials: Q
authors.lastname: Tang
authors.affiliation: College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou 215163, China.
authors.forename: Xiaohong
authors.initials: X
authors.lastname: Li
authors.affiliation: College of Physics, Optoelectronics and Energy & Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University , Suzhou 215006, China.
authors.forename: Meirong
authors.initials: M
authors.lastname: Zhang
authors.affiliation: College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou 215163, China.
authors.forename: Yingbo
authors.initials: Y
authors.lastname: Wan
authors.affiliation: College of Physics, Optoelectronics and Energy & Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University , Suzhou 215006, China.
authors.forename: Lai
authors.initials: L
authors.lastname: Feng
authors.affiliation: College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou 215163, China.
authors.forename: Ning
authors.initials: N
authors.lastname: Chen
authors.affiliation: Department of Chemistry and Biochemistry, University of Arizona , Tucson, Arizona 85721-0041, United States.
authors.forename: Zdeněk
authors.initials: Z
authors.lastname: Slanina
authors.affiliation: Department of Chemistry and Biochemistry, University of Arizona , Tucson, Arizona 85721-0041, United States.
authors.forename: Ludwik
authors.initials: L
authors.lastname: Adamowicz
authors.affiliation: Department of Physical and Macromolecular Chemistry, Faculty of Science, Charles University in Prague , Albertov 6, 128 43 Praha 2, Czech Republic.
authors.forename: Filip
authors.initials: F
authors.lastname: Uhlík