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The bottom-up synthesis of strained hollow cage structures, such as fullerenes, using traditional thermal or photochemical methods remains one of the most challenging tasks in organic chemistry. Here, we demonstrate the synthetic use of an electron beam by in-depth single-molecule atomic resolution time-resolved transmission electron microscopy studies to induce the formation of a doubly-holed fullerene-porphyrin cage structure from a well-defined benzoporphyrin precursor deposited on graphene. Through real-time imaging, we analyze the hybrid’s peculiar ability to host up to two Pb atoms and subsequently gain insights into the dynamics of the Pb–Pb binding motif in this exotic organometallic cage structure. With the help of density functional theory calculations and image simulations, we identify two central mechanisms responsible for the molecular transformations. Importantly, not only the fast primary electrons appear to induce chemical reactions, but also the much slower secondary electrons, which accumulate in the periphery of the irradiated area.

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• In Copyright
  

Keyword: molecular imaging, radiation chemistry, cinematic chemistry, single-molecule dynamics, DFT-modeling, transmission electron microscopy

Date published: 2023-06-29

Publisher: Springer Science and Business Media LLC

Journal:

• Nature Chemistry (ISSN: 17554349) vol. 15 p. 1444-1451

Funding:

Manuscript type: Author's version (Accepted manuscript)

MDR DOI: https://doi.org/10.48505/nims.4241

First published URL: https://doi.org/10.1038/s41557-023-01261-7

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Updated at: 2024-01-05 22:12:51 +0900

Published on MDR: 2024-01-11 08:30:22 +0900