Time-resolved imaging and analysis of the electron beam-induced formation of an open-cage metallo-azafullerene

The visualization of single-molecule reactions provides crucial insights into chemical processes, and the ability to do so has grown with the advances in high-resolution transmission electron microscopy. There is currently a limited mechanistic understanding of chemical reactions under the electron beam. However, such reactions may enable synthetic methodologies that cannot be accessed by traditional organic chemistry methods. Here we demonstrate the synthetic use of the electron beam, by in-depth single-molecule, atomic-resolution, time-resolved transmission electron microscopy studies, in inducing the formation of a doubly holed fullerene-porphyrin cage structure from a well-defined benzoporphyrin precursor deposited on graphene. Through real-time imaging, we analyse the hybrid's ability to host up to two Pb atoms, and subsequently probe the dynamics of the Pb-Pb binding motif in this exotic metallo-organic cage structure. Through simulation, we conclude that the secondary electrons, which accumulate in the periphery of the irradiated area, can also initiate chemical reactions. Consequently, designing advanced carbon nanostructures by electron-beam lithography will depend on the understanding and limitations of molecular radiation chemistry.

Automated summary

The visualization of single-molecule reactions using high-resolution transmission electron microscopy provides important insights into chemical processes. This study demonstrates the synthetic use of the electron beam by inducing the formation of a doubly holed fullerene-porphyrin cage structure through in-depth time-resolved transmission electron microscopy studies. The findings suggest that secondary electrons in the irradiated area can initiate chemical reactions, highlighting the importance of understanding molecular radiation chemistry for designing advanced carbon nanostructures by electron-beam lithography.