Breaking Strong Alkynyl-Phenyl Bonds: Poly(para-phenylene ethynylene)s under Mechanical Stress [data]

DOI

Stronger chemical bonds withstand higher mechanical forces, and thus, 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-phenyleneethynylene)s (PPEs), a fully conjugated polymer. In a scale-bridging approach using electron-paramagnetic resonance spectroscopy and gel permeation chromatography of cryo-milled 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 efficient stress concentration.

Identifier
DOI https://doi.org/10.11588/data/YPHTIY
Related Identifier IsCitedBy https://doi.org/10.1021/jacs.4c08765
Metadata Access https://heidata.uni-heidelberg.de/oai?verb=GetRecord&metadataPrefix=oai_datacite&identifier=doi:10.11588/data/YPHTIY
Provenance
Creator Elter, Maximilian ORCID logo; Brosz, Matthias ORCID logo; Sucerquia, Daniel ORCID logo; Kuzhelev, Andrei ORCID logo; Kiesewetter, Denis C.; Kurth, Markus ORCID logo; Dreuw, Andreas; Prisner, Thomas F. ORCID logo; Freudenberg, Jan (ORCID: 0000-0003-0998-693X); Bunz, Uwe H. F. ORCID logo; Gräter, Frauke ORCID logo
Publisher heiDATA
Contributor Elter, Maximilian
Publication Year 2024
Funding Reference Deutsche Forschungsgemeinschaft EXC-2082/1-390761711 ; Klaus Tschira Foundation SIMPLAIX
Rights CC BY 4.0; info:eu-repo/semantics/openAccess; http://creativecommons.org/licenses/by/4.0
OpenAccess true
Contact Elter, Maximilian (Heidelberg university [enter full affiliation])
Representation
Resource Type Dataset
Format application/zip; text/plain
Size 2568426; 833356; 44977; 1451423; 96769; 671; 22533; 1303973
Version 1.0
Discipline Chemistry; Natural Sciences