Direct C2 Bottom-Up Assembly: Unraveling the Formation Mechanism of [10,0] Metallofullertubes, Ce2@C40+40+20n Series

Abstract The preparation of metallofullertubes remains challenging, and elucidating the atomistic details of their formation is critical for achieving controlled synthesis. Inspired by recent experimental advances (Angew. Chem. Int. Ed. 2022, 61, e202116854), we present a density functional theory (DFT) investigation into the origin of Ce2@D5(450)-C100 derived from the experimentally characterized Ce2@Ih(7)-C80 and Ce2@D5h(6)-C80 structures. We uncover a distinct growth pathway in which additional C20 rings form through ten consecutive C2 insertions, notably without invoking Stone–Wales rearrangements. Moreover, our theoretical studies summarize the [10,0] metallofullertube Ce2@C40+40+20n series and predict several unreported stable isomers of [10,0] metallofullertubes, such as Ce2@D5d(10765)-C120 and Ce2@D5h(10766)-C120. These findings provide fundamental mechanistic insights into metallofullertube assembly and establish guiding principles for the rational design of next-generation nanomaterials.