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Breaking strong alkynyl-phenyl bonds: poly(para-phenylene ethynylene)s under mechanical stress

Stronger chemical bonds withstand higher mechanical forces; thus, the rupture of single bonds is preferred over the rupture of double or triple bonds or aromatic rings. We investigated bond scission in poly(dialkyl-p-phenylene ethynylene)s (PPEs), a fully conjugated polymer. In a scale-bridging appr...

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Main Authors: Elter, Maximilian (Author) , Brosz, Matthias (Author) , Sucerquia, Daniel (Author) , Kuzhelev, Andrei (Author) , Kiesewetter, Denis (Author) , Kurth, Markus (Author) , Dreuw, Andreas (Author) , Prisner, Thomas F. (Author) , Freudenberg, Jan (Author) , Bunz, Uwe H. F. (Author) , Gräter, Frauke (Author)
Format: Article (Journal)
Language:English
Published: 2024
In: Journal of the American Chemical Society
Year: 2024, Volume: 146, Issue: 40, Pages: 27594-27599
ISSN:1520-5126
DOI:10.1021/jacs.4c08765
Online Access:Verlag, kostenfrei, Volltext: https://doi.org/10.1021/jacs.4c08765
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Author Notes:Maximilian Elter, Matthias Brosz, Daniel Sucerquia, Andrei Kuzhelev, Denis C. Kiesewetter, Markus Kurth, Andreas Dreuw, Thomas F. Prisner, Jan Freudenberg, Uwe H. F. Bunz, and Frauke Gräter
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Summary:Stronger chemical bonds withstand higher mechanical forces; thus, the rupture of single bonds is preferred over the rupture of double or triple bonds or aromatic rings. We investigated bond scission in poly(dialkyl-p-phenylene ethynylene)s (PPEs), a fully conjugated polymer. In a scale-bridging approach using electron-paramagnetic resonance spectroscopy and gel permeation chromatography of cryomilled samples, in combination with density functional theory calculations and coarse-grained simulations, we conclude that mechanical force cleaves the sp-sp2 bond of PPEs (bond dissociation energy as high as 600 kJ mol-1). Bond scission primarily occurs in shear bands with locally increased shear stresses. The scission occurs in the middle of the PPE chains. Breaking sp-sp2 bonds into free radicals thus is feasible but requires significant mechanical force and an efficient stress concentration.
Item Description:Online veröffentlicht: 27. September 2024
Gesehen am 19.03.2025
Physical Description:Online Resource
ISSN:1520-5126
DOI:10.1021/jacs.4c08765

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