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Stop-frame filming and discovery of reactions at the single-molecule level by transmission electron microscopy

Chamberlain, Thomas W.; Biskupek, Johannes; Skowron, Stephen T.; Markevich, Alexander V.; Kurasch, Simon; Reimer, Oliver; Walker, Kate E.; Rance, Graham A.; Xinliang, Feng; M�llen, Klaus; Turchanin, Andrey; Lebedeva, Maria A.; Majouga, Alexander G.; Nenajdenko, Valentin G.; Kaiser, Ute; Besley, Elena; Khlobystov, Andrei N.

Authors

Thomas W. Chamberlain

Johannes Biskupek

Stephen T. Skowron

Alexander V. Markevich

Simon Kurasch

Oliver Reimer

Kate E. Walker

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GRAHAM RANCE Graham.Rance@nottingham.ac.uk
Senior Research Fellow

Feng Xinliang

Klaus M�llen

Andrey Turchanin

Maria A. Lebedeva

Alexander G. Majouga

Valentin G. Nenajdenko

Ute Kaiser



Abstract

We report an approach – named chemTEM – to follow chemical transformations at the single-molecule level with the electron beam of a transmission electron microscope (TEM) applied as both a tuneable source of energy and a sub-Angstrom imaging probe. Deposited on graphene, disk-shaped perchlorocoronene molecules are precluded from intermolecular interactions. This allows monomolecular transformations to be studied at the single-molecule level in real time and reveals chlorine elimination and reactive aryne formation as a key initial stage of multi-step reactions initiated by the 80 keV e-beam. Under the same conditions, perchlorocoronene confined within a nanotube cavity, where the molecules are situated in very close proximity to each other, enables imaging of intermolecular reactions, starting with the Diels-Alder cycloaddition of a generated aryne, followed by rearrangement of the angular adduct to a planar polyaromatic structure and the formation of a perchlorinated zigzag nanoribbon of graphene as the final product. ChemTEM enables the entire process of polycondensation, including the formation of metastable intermediates, to be captured in a one-shot ‘movie’. A molecule with a similar size and shape but with a different chemical composition, octathio[8]circulene, under the same conditions undergoes another type of polycondensation via thiyl biradical generation and subsequent reaction leading to polythiophene nanoribbons with irregular edges incorporating bridging sulphur atoms. Graphene or carbon nanotubes supporting the individual molecules during chemTEM studies ensure that the elastic interactions of the molecules with the e-beam are the dominant forces that initiate and drive the reactions we image. Our ab initio DFT calculations explicitly incorporating the e-beam in the theoretical model correlate with the chemTEM observations and give a mechanism for direct control not only of the type of the reaction but also of the reaction rate. Selection of the appropriate e-beam energy and control of the dose rate in chemTEM enabled imaging of reactions on a timeframe commensurate with TEM image capture rates, revealing atomistic mechanisms of previously unknown processes.

Citation

Chamberlain, T. W., Biskupek, J., Skowron, S. T., Markevich, A. V., Kurasch, S., Reimer, O., …Khlobystov, A. N. (2017). Stop-frame filming and discovery of reactions at the single-molecule level by transmission electron microscopy. ACS Nano, 11(3), 2509-2520. https://doi.org/10.1021/acsnano.6b08228

Journal Article Type Article
Acceptance Date Feb 13, 2017
Online Publication Date Feb 13, 2017
Publication Date Mar 30, 2017
Deposit Date Feb 20, 2017
Publicly Available Date Mar 28, 2024
Journal ACS Nano
Print ISSN 1936-0851
Electronic ISSN 1936-086X
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 11
Issue 3
Pages 2509-2520
DOI https://doi.org/10.1021/acsnano.6b08228
Keywords transmission electron microscopy, carbon nanotube, graphene, single-moleculeimaging, single-molecule reaction
Public URL https://nottingham-repository.worktribe.com/output/845986
Publisher URL http://pubs.acs.org/doi/abs/10.1021/acsnano.6b08228

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