Entropy-Driven Selectivity for Chain Scission: Where Macromolecules Cleave
Kai Pahnke
Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstrasse 18, 76131 Karlsruhe, Germany
Institut für Biologische Grenzflächen, Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany
Search for more papers by this authorJosef Brandt
Leibniz-Institut für Polymerforschung Dresden, Hohe Strasse 6, 01069 Dresden, Germany
Technische Universität Dresden, 01062 Dresden, Germany
Search for more papers by this authorDr. Ganna Gryn'ova
ARC Centre of Excellence for Electromaterials Science, Research School of Chemistry, Australian National University (ANU), Canberra, ACT, 0200 Australia
Ecole polytechnique fédérale de Lausanne, Switzerland
Search for more papers by this authorDr. Ching Y. Lin
ARC Centre of Excellence for Electromaterials Science, Research School of Chemistry, Australian National University (ANU), Canberra, ACT, 0200 Australia
Search for more papers by this authorDr. Ozcan Altintas
Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstrasse 18, 76131 Karlsruhe, Germany
Institut für Biologische Grenzflächen, Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany
Search for more papers by this authorDr. Friedrich G. Schmidt
Evonik Industries AG, Paul-Baumann-Strasse 1, 45764 Marl, Germany
Search for more papers by this authorCorresponding Author
Dr. Albena Lederer
Leibniz-Institut für Polymerforschung Dresden, Hohe Strasse 6, 01069 Dresden, Germany
Technische Universität Dresden, 01062 Dresden, Germany
Search for more papers by this authorCorresponding Author
Prof. Michelle L. Coote
ARC Centre of Excellence for Electromaterials Science, Research School of Chemistry, Australian National University (ANU), Canberra, ACT, 0200 Australia
Search for more papers by this authorCorresponding Author
Prof. Christopher Barner-Kowollik
Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstrasse 18, 76131 Karlsruhe, Germany
Institut für Biologische Grenzflächen, Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany
Search for more papers by this authorKai Pahnke
Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstrasse 18, 76131 Karlsruhe, Germany
Institut für Biologische Grenzflächen, Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany
Search for more papers by this authorJosef Brandt
Leibniz-Institut für Polymerforschung Dresden, Hohe Strasse 6, 01069 Dresden, Germany
Technische Universität Dresden, 01062 Dresden, Germany
Search for more papers by this authorDr. Ganna Gryn'ova
ARC Centre of Excellence for Electromaterials Science, Research School of Chemistry, Australian National University (ANU), Canberra, ACT, 0200 Australia
Ecole polytechnique fédérale de Lausanne, Switzerland
Search for more papers by this authorDr. Ching Y. Lin
ARC Centre of Excellence for Electromaterials Science, Research School of Chemistry, Australian National University (ANU), Canberra, ACT, 0200 Australia
Search for more papers by this authorDr. Ozcan Altintas
Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstrasse 18, 76131 Karlsruhe, Germany
Institut für Biologische Grenzflächen, Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany
Search for more papers by this authorDr. Friedrich G. Schmidt
Evonik Industries AG, Paul-Baumann-Strasse 1, 45764 Marl, Germany
Search for more papers by this authorCorresponding Author
Dr. Albena Lederer
Leibniz-Institut für Polymerforschung Dresden, Hohe Strasse 6, 01069 Dresden, Germany
Technische Universität Dresden, 01062 Dresden, Germany
Search for more papers by this authorCorresponding Author
Prof. Michelle L. Coote
ARC Centre of Excellence for Electromaterials Science, Research School of Chemistry, Australian National University (ANU), Canberra, ACT, 0200 Australia
Search for more papers by this authorCorresponding Author
Prof. Christopher Barner-Kowollik
Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstrasse 18, 76131 Karlsruhe, Germany
Institut für Biologische Grenzflächen, Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany
Search for more papers by this authorGraphical Abstract
Middle versus end? When all other conditions are equal, bond cleavage in the middle of molecules is entropically much more favored than bond cleavage at the end. Experimental and theoretical approaches were used to study the selectivity of bond cleavage or dissociation of both covalent and supramolecular adducts. The findings have extensive implications for other fields of chemistry.
Abstract
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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