Open AccessIsomeric Sc2O@C78 Related by a Single-Step Stone–Wales Transformation: Key Links in an Unprecedented Fullerene Formation Pathway
Author(s) -
Yajuan Hao,
Qiangqiang Tang,
Xiaohong Li,
Meirong Zhang,
Yingbo Wan,
Lai Feng,
Ning Chen,
Zdeněk Slanina,
Ludwik Adamowicz,
Filip Uhlı́k
Publication year - 2016
Publication title -
inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 233
eISSN - 1520-510X
pISSN - 0020-1669
DOI - 10.1021/acs.inorgchem.6b01894
Subject(s) - fullerene , chemistry , electrochemistry , solvent , crystallography , combinatorial chemistry , computational chemistry , stereochemistry , nanotechnology , organic chemistry , materials science , electrode
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 C 2 losses 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 Sc 2 O@C 2v (3)-C 78 and Sc 2 O@D 3h (5)-C 78 , which are closely related via a single-step Stone-Wales (SW) transformation. More importantly, these novel Sc 2 O@C 78 isomers represent the key links in a well-defined formation pathway for the majority of solvent-extractable clusterfullerenes Sc 2 O@C 2n (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 Sc 2 O@C 78 isomers, which may rationalize the established fullerene formation pathway. Additional characterizations demonstrate that these Sc 2 O@C 78 isomers feature different energy bandgaps and electrochemical behaviors, indicating the impact of SW defects on the energetic and electrochemical characteristics of metallofullerenes.