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Radical‐Pairing Interactions in a Molecular Switch Evidenced by Ion Mobility Spectrometry and Infrared Ion Spectroscopy
Author(s) -
Hanozin Emeline,
Mignolet Benoit,
Martens Jonathan,
Berden Giel,
Sluysmans Damien,
Duwez AnneSophie,
Stoddart J. Fraser,
Eppe Gauthier,
Oomens Jos,
De Pauw Edwin,
Morsa Denis
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202014728
Subject(s) - chemistry , infrared spectroscopy , intramolecular force , ion , molecular switch , mass spectrometry , infrared , electron transfer dissociation , spectroscopy , photochemistry , chemical physics , molecule , tandem mass spectrometry , stereochemistry , physics , organic chemistry , chromatography , quantum mechanics , optics
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.