Isomeric Sc2O@C78 Related 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 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 Sc2O@C-2v(3)-C-78 and Sc2O@D-3h(5)-C-78, which are closely related via a single-step Stone Wales (SW) transformation.
More importantly, these novel Sc2O@C-78 isomers represent the key links in a well-defined formation pathway for the majority of solvent-extractable clusterfullerenes Sc2O@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 Sc2O@C-78 isomers, which may rationalize the established fullerene formation pathway.
Additional characterizations demonstrate that these Sc2O@C-78 isomers feature different energy bandgaps and electrochemical behaviors, indicating the impact of SW defects on the energetic and electrochemical characteristics of metallofullerenes.