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Entropy-Driven Selectivity for Chain Scission: Where Macromolecules Cleave

Pahnke, Kai; Brandt, Josef; Gryn'ova, Ganna; Lin, Ching Y; Altintas, Ozcan; Schmidt, Friedrich G; Lederer, Albena; Coote, Michelle; Barner-Kowollik, Christopher

Description

We show that, all other conditions being equal, bond cleavage in the middle of molecules is entropically much more favored than bond cleavage at the end. Multiple experimental and theoretical approaches have been used to study the selectivity for bond cleavage or dissociation in the middle versus the end of both covalent and supramolecular adducts and the extensive implications for other fields of chemistry including, e.g., chain transfer, polymer degradation, and control agent addition are...[Show more]

dc.contributor.authorPahnke, Kai
dc.contributor.authorBrandt, Josef
dc.contributor.authorGryn'ova, Ganna
dc.contributor.authorLin, Ching Y
dc.contributor.authorAltintas, Ozcan
dc.contributor.authorSchmidt, Friedrich G
dc.contributor.authorLederer, Albena
dc.contributor.authorCoote, Michelle
dc.contributor.authorBarner-Kowollik, Christopher
dc.date.accessioned2020-09-02T03:14:51Z
dc.date.available2020-09-02T03:14:51Z
dc.identifier.issn1433-7851
dc.identifier.urihttp://hdl.handle.net/1885/209219
dc.description.abstractWe show that, all other conditions being equal, bond cleavage in the middle of molecules is entropically much more favored than bond cleavage at the end. Multiple experimental and theoretical approaches have been used to study the selectivity for bond cleavage or dissociation in the middle versus the end of both covalent and supramolecular adducts and the extensive implications for other fields of chemistry including, e.g., chain transfer, polymer degradation, and control agent addition are discussed. The observed effects, which are a consequence of the underlying entropic factors, were predicted on the basis of simple theoretical models and demonstrated via high-temperature (HT) NMR spectroscopy of self-assembled supramolecular diblock systems as well as temperature-dependent size-exclusion chromatography (TD SEC) of covalently bonded Diels-Alder step-growth polymers.
dc.description.sponsorshipC.B.-K. additionally acknowledges funding from the KIT via the Helmholtz association (BIFTM and STN programs) as well as the German Research Council (DFG). M.L.C. acknowledges generous allocations of supercomputing time on the National Facility of the National Computationa Infrastructure and an Australian Research Council Future Fellowship.
dc.format.mimetypeapplication/pdf
dc.language.isoen_AU
dc.publisherWiley
dc.rights© 2016 Wiley-VCH Verlag GmbH &Co. KGaA, Weinheim
dc.sourceAngewandte Chemie (International ed. in English)
dc.subjectcycloadditions
dc.subjectentropic effects
dc.subjectpolymers
dc.subjectsupramolecular chemistry
dc.subjectthermodynamics
dc.titleEntropy-Driven Selectivity for Chain Scission: Where Macromolecules Cleave
dc.typeJournal article
local.identifier.citationvolume55
dc.date.issued2016-01-22
local.publisher.urlhttps://www.wiley.com/en-gb
local.type.statusAccepted Version
local.contributor.affiliationGryn'ova, A., Research School of Chemistry, The Australian National University
local.contributor.affiliationLin, C. Y., Research School of Chemistry, The Australian National University
local.contributor.affiliationCoote, Michelle, Research School of Chemistry, The Australian National University
dc.relationhttp://purl.org/au-research/grants/arc/CE140100012
local.identifier.essn1521-3773
local.bibliographicCitation.issue4
local.bibliographicCitation.startpage1514
local.bibliographicCitation.lastpage1518
local.identifier.doi10.1002/anie.201508531
dcterms.accessRightsOpen Access
dc.provenancehttps://v2.sherpa.ac.uk/id/publication/1320..."The Accepted Version can be archived in a Non-Commercial Institutional Repository. 12 months embargo" from SHERPA/RoMEO site (as at 2/09/2020). This is the peer reviewed version of the following article: [Pahnke, Kai, et al. "Entropy‐Driven Selectivity for Chain Scission: Where Macromolecules Cleave." Angewandte Chemie International Edition 55.4 (2016): 1514-1518.], which has been published in final form at [https://dx.doi.org/10.1002/anie.201508531]. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions
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