Radical-Pairing Interactions in a Molecular Switch Evidenced by Ion Mobility Spectrometry and Infrared Ion Spectroscopy

Emeline Hanozin; Benoit Mignolet; Jonathan Martens; Giel Berden; Damien Sluysmans; Anne Sophie Duwez; J. Fraser Stoddart; Gauthier Eppe; Jos Oomens; Edwin De Pauw; Denis Morsa

doi:10.1002/anie.202014728

Radical-Pairing Interactions in a Molecular Switch Evidenced by Ion Mobility Spectrometry and Infrared Ion Spectroscopy

Emeline Hanozin, Benoit Mignolet, Jonathan Martens, Giel Berden, Damien Sluysmans, Anne Sophie Duwez, J. Fraser Stoddart, Gauthier Eppe, Jos Oomens, Edwin De Pauw, Denis Morsa^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

11 Scopus citations

Abstract

The digital revolution sets a milestone in the progressive miniaturization of working devices and in the underlying advent of molecular machines. Foldamers involving mechanically entangled components with modular secondary structures are among the most promising designs for molecular switch-based applications. Characterizing the nature and dynamics of their intramolecular network following the application of a stimulus is the key to their performance. Here, we use non-dissociative electron transfer as a reductive stimulus in the gas phase and probe the consecutive co-conformational transitions of a donor-acceptor oligorotaxane foldamer using electrospray mass spectrometry interfaced with ion mobility and infrared ion spectroscopy. A comparison of collision cross section distributions for analogous closed-shell and radical molecular ions sheds light on their respective formation energetics, while variations in their respective infrared absorption bands evidence changes in intramolecular organization as the foldamer becomes more compact. These differences are compatible with the advent of radical-pairing interactions.

Original language	English (US)
Pages (from-to)	10049-10055
Number of pages	7
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	18
DOIs	https://doi.org/10.1002/anie.202014728
State	Published - Apr 26 2021

Funding

The research leading to these results has received funding from LASERLAB‐EUROPE (grant agreement no. 654148, European Union's Horizon 2020 research and innovation program). The authors gratefully acknowledge the Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO) for the support of the FELIX Laboratory. Computational resources have been provided by the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds de la Recherche Scientifique de Belgique (F.R.S.‐FNRS) under Grant No. 2.5020.11 and by the Walloon Region. The authors thank Dr. Zhixue Zhu for the synthesis of the oligorotaxane foldamer. J.F.S. thanks Northwestern University for its continuing support of his research. Prof. Loïc Quinton, Prof. Bernard Leyh, Dr. Johann Far and Dr. Christopher Kune (University of Liège, Belgium) are acknowledged for discussions on the results. D.S. is a Post‐doctoral researcher of the FRS‐FNRS. The research leading to these results has received funding from LASERLAB-EUROPE (grant agreement no. 654148, European Union's Horizon 2020 research and innovation program). The authors gratefully acknowledge the Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO) for the support of the FELIX Laboratory. Computational resources have been provided by the Consortium des ?quipements de Calcul Intensif (C?CI), funded by the Fonds de la Recherche Scientifique de Belgique (F.R.S.-FNRS) under Grant No. 2.5020.11 and by the Walloon Region. The authors thank Dr. Zhixue Zhu for the synthesis of the oligorotaxane foldamer. J.F.S. thanks Northwestern University for its continuing support of his research. Prof. Lo?c Quinton, Prof. Bernard Leyh, Dr. Johann Far and Dr. Christopher Kune (University of Li?ge, Belgium) are acknowledged for discussions on the results. D.S. is a Post-doctoral researcher of the FRS-FNRS.

Keywords

donor-acceptor foldamer
electron transfer
infrared spectroscopy
ion mobility
mass spectrometry

ASJC Scopus subject areas

General Chemistry
Catalysis

Access to Document

10.1002/anie.202014728

Cite this

Hanozin, E., Mignolet, B., Martens, J., Berden, G., Sluysmans, D., Duwez, A. S., Stoddart, J. F., Eppe, G., Oomens, J., De Pauw, E., & Morsa, D. (2021). Radical-Pairing Interactions in a Molecular Switch Evidenced by Ion Mobility Spectrometry and Infrared Ion Spectroscopy. Angewandte Chemie - International Edition, 60(18), 10049-10055. https://doi.org/10.1002/anie.202014728

@article{e7350973365c42a1b27d403af6b845b6,

title = "Radical-Pairing Interactions in a Molecular Switch Evidenced by Ion Mobility Spectrometry and Infrared Ion Spectroscopy",

abstract = "The digital revolution sets a milestone in the progressive miniaturization of working devices and in the underlying advent of molecular machines. Foldamers involving mechanically entangled components with modular secondary structures are among the most promising designs for molecular switch-based applications. Characterizing the nature and dynamics of their intramolecular network following the application of a stimulus is the key to their performance. Here, we use non-dissociative electron transfer as a reductive stimulus in the gas phase and probe the consecutive co-conformational transitions of a donor-acceptor oligorotaxane foldamer using electrospray mass spectrometry interfaced with ion mobility and infrared ion spectroscopy. A comparison of collision cross section distributions for analogous closed-shell and radical molecular ions sheds light on their respective formation energetics, while variations in their respective infrared absorption bands evidence changes in intramolecular organization as the foldamer becomes more compact. These differences are compatible with the advent of radical-pairing interactions.",

keywords = "donor-acceptor foldamer, electron transfer, infrared spectroscopy, ion mobility, mass spectrometry",

author = "Emeline Hanozin and Benoit Mignolet and Jonathan Martens and Giel Berden and Damien Sluysmans and Duwez, \{Anne Sophie\} and Stoddart, \{J. Fraser\} and Gauthier Eppe and Jos Oomens and \{De Pauw\}, Edwin and Denis Morsa",

note = "Funding Information: The research leading to these results has received funding from LASERLAB‐EUROPE (grant agreement no. 654148, European Union's Horizon 2020 research and innovation program). The authors gratefully acknowledge the Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO) for the support of the FELIX Laboratory. Computational resources have been provided by the Consortium des {\'E}quipements de Calcul Intensif (C{\'E}CI), funded by the Fonds de la Recherche Scientifique de Belgique (F.R.S.‐FNRS) under Grant No. 2.5020.11 and by the Walloon Region. The authors thank Dr. Zhixue Zhu for the synthesis of the oligorotaxane foldamer. J.F.S. thanks Northwestern University for its continuing support of his research. Prof. Lo{\"i}c Quinton, Prof. Bernard Leyh, Dr. Johann Far and Dr. Christopher Kune (University of Li{\`e}ge, Belgium) are acknowledged for discussions on the results. D.S. is a Post‐doctoral researcher of the FRS‐FNRS. Funding Information: The research leading to these results has received funding from LASERLAB-EUROPE (grant agreement no. 654148, European Union's Horizon 2020 research and innovation program). The authors gratefully acknowledge the Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO) for the support of the FELIX Laboratory. Computational resources have been provided by the Consortium des ?quipements de Calcul Intensif (C?CI), funded by the Fonds de la Recherche Scientifique de Belgique (F.R.S.-FNRS) under Grant No. 2.5020.11 and by the Walloon Region. The authors thank Dr. Zhixue Zhu for the synthesis of the oligorotaxane foldamer. J.F.S. thanks Northwestern University for its continuing support of his research. Prof. Lo?c Quinton, Prof. Bernard Leyh, Dr. Johann Far and Dr. Christopher Kune (University of Li?ge, Belgium) are acknowledged for discussions on the results. D.S. is a Post-doctoral researcher of the FRS-FNRS. Publisher Copyright: {\textcopyright} 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH",

year = "2021",

month = apr,

day = "26",

doi = "10.1002/anie.202014728",

language = "English (US)",

volume = "60",

pages = "10049--10055",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

number = "18",

}

Hanozin, E, Mignolet, B, Martens, J, Berden, G, Sluysmans, D, Duwez, AS, Stoddart, JF, Eppe, G, Oomens, J, De Pauw, E & Morsa, D 2021, 'Radical-Pairing Interactions in a Molecular Switch Evidenced by Ion Mobility Spectrometry and Infrared Ion Spectroscopy', Angewandte Chemie - International Edition, vol. 60, no. 18, pp. 10049-10055. https://doi.org/10.1002/anie.202014728

TY - JOUR

T1 - Radical-Pairing Interactions in a Molecular Switch Evidenced by Ion Mobility Spectrometry and Infrared Ion Spectroscopy

AU - Hanozin, Emeline

AU - Mignolet, Benoit

AU - Martens, Jonathan

AU - Berden, Giel

AU - Sluysmans, Damien

AU - Duwez, Anne Sophie

AU - Stoddart, J. Fraser

AU - Eppe, Gauthier

AU - Oomens, Jos

AU - De Pauw, Edwin

AU - Morsa, Denis

N1 - Funding Information: The research leading to these results has received funding from LASERLAB‐EUROPE (grant agreement no. 654148, European Union's Horizon 2020 research and innovation program). The authors gratefully acknowledge the Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO) for the support of the FELIX Laboratory. Computational resources have been provided by the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds de la Recherche Scientifique de Belgique (F.R.S.‐FNRS) under Grant No. 2.5020.11 and by the Walloon Region. The authors thank Dr. Zhixue Zhu for the synthesis of the oligorotaxane foldamer. J.F.S. thanks Northwestern University for its continuing support of his research. Prof. Loïc Quinton, Prof. Bernard Leyh, Dr. Johann Far and Dr. Christopher Kune (University of Liège, Belgium) are acknowledged for discussions on the results. D.S. is a Post‐doctoral researcher of the FRS‐FNRS. Funding Information: The research leading to these results has received funding from LASERLAB-EUROPE (grant agreement no. 654148, European Union's Horizon 2020 research and innovation program). The authors gratefully acknowledge the Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO) for the support of the FELIX Laboratory. Computational resources have been provided by the Consortium des ?quipements de Calcul Intensif (C?CI), funded by the Fonds de la Recherche Scientifique de Belgique (F.R.S.-FNRS) under Grant No. 2.5020.11 and by the Walloon Region. The authors thank Dr. Zhixue Zhu for the synthesis of the oligorotaxane foldamer. J.F.S. thanks Northwestern University for its continuing support of his research. Prof. Lo?c Quinton, Prof. Bernard Leyh, Dr. Johann Far and Dr. Christopher Kune (University of Li?ge, Belgium) are acknowledged for discussions on the results. D.S. is a Post-doctoral researcher of the FRS-FNRS. Publisher Copyright: © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH

PY - 2021/4/26

Y1 - 2021/4/26

N2 - The digital revolution sets a milestone in the progressive miniaturization of working devices and in the underlying advent of molecular machines. Foldamers involving mechanically entangled components with modular secondary structures are among the most promising designs for molecular switch-based applications. Characterizing the nature and dynamics of their intramolecular network following the application of a stimulus is the key to their performance. Here, we use non-dissociative electron transfer as a reductive stimulus in the gas phase and probe the consecutive co-conformational transitions of a donor-acceptor oligorotaxane foldamer using electrospray mass spectrometry interfaced with ion mobility and infrared ion spectroscopy. A comparison of collision cross section distributions for analogous closed-shell and radical molecular ions sheds light on their respective formation energetics, while variations in their respective infrared absorption bands evidence changes in intramolecular organization as the foldamer becomes more compact. These differences are compatible with the advent of radical-pairing interactions.

AB - The digital revolution sets a milestone in the progressive miniaturization of working devices and in the underlying advent of molecular machines. Foldamers involving mechanically entangled components with modular secondary structures are among the most promising designs for molecular switch-based applications. Characterizing the nature and dynamics of their intramolecular network following the application of a stimulus is the key to their performance. Here, we use non-dissociative electron transfer as a reductive stimulus in the gas phase and probe the consecutive co-conformational transitions of a donor-acceptor oligorotaxane foldamer using electrospray mass spectrometry interfaced with ion mobility and infrared ion spectroscopy. A comparison of collision cross section distributions for analogous closed-shell and radical molecular ions sheds light on their respective formation energetics, while variations in their respective infrared absorption bands evidence changes in intramolecular organization as the foldamer becomes more compact. These differences are compatible with the advent of radical-pairing interactions.

KW - donor-acceptor foldamer

KW - electron transfer

KW - infrared spectroscopy

KW - ion mobility

KW - mass spectrometry

UR - http://www.scopus.com/inward/record.url?scp=85103162101&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85103162101&partnerID=8YFLogxK

U2 - 10.1002/anie.202014728

DO - 10.1002/anie.202014728

M3 - Article

C2 - 33561311

AN - SCOPUS:85103162101

SN - 1433-7851

VL - 60

SP - 10049

EP - 10055

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 18

ER -

Radical-Pairing Interactions in a Molecular Switch Evidenced by Ion Mobility Spectrometry and Infrared Ion Spectroscopy

Abstract

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this