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 L., & Barner-Kowollik, Christopher (2016) Entropy-driven selectivity for chain scission: Where macromolecules cleave. Angewandte Chemie International Edition, 55(4), pp. 1514-1518.

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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 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.

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3 citations in Scopus
3 citations in Web of Science®
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ID Code: 97005
Item Type: Journal Article
Refereed: Yes
Keywords: cycloadditions; entropic effects; polymers; supramolecular chemistry; thermodynamics
DOI: 10.1002/anie.201508531
ISSN: 1521-3773
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Copyright Owner: Copyright 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Deposited On: 11 Aug 2016 23:19
Last Modified: 15 Aug 2016 00:08

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