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Brancart J, Van Damme J, Du Prez F, et al. Thermal dissociation of anthracene photodimers in the condensed state: kinetic evaluation and complex phase behaviour. Phys Chem Chem Phys. 2020;22(30):17306-17313doi: 10.1039/d0cp03165h.
Brancart, J., Van Damme, J., Du Prez, F., & Van Assche, G. (2020). Thermal dissociation of anthracene photodimers in the condensed state: kinetic evaluation and complex phase behaviour. Physical chemistry chemical physics : PCCP, 22(30), 17306-17313. https://doi.org/10.1039/d0cp03165h
Brancart, Joost, et al. "Thermal dissociation of anthracene photodimers in the condensed state: kinetic evaluation and complex phase behaviour." Physical chemistry chemical physics : PCCP vol. 22,30 (2020): 17306-17313. doi: https://doi.org/10.1039/d0cp03165h
Brancart J, Van Damme J, Du Prez F, Van Assche G. Thermal dissociation of anthracene photodimers in the condensed state: kinetic evaluation and complex phase behaviour. Phys Chem Chem Phys. 2020 Aug 05;22(30):17306-17313. doi: 10.1039/d0cp03165h. PMID: 32687137.
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Phys Chem Chem Phys. 2020 Aug 05;22(30):17306-17313. doi: 10.1039/d0cp03165h.

Thermal dissociation of anthracene photodimers in the condensed state: kinetic evaluation and complex phase behaviour.

Physical chemistry chemical physics : PCCP

Joost Brancart, Jonas Van Damme, Filip Du Prez, Guy Van Assche

Affiliations

  1. Physical Chemistry and Polymer Science, Department of Materials and Chemistry, Vrije Universiteit Brussel, Pleinlaan 2, B-1050 Brussels, Belgium. [email protected].
  2. Polymer Chemistry Research Group, Centre of Macromolecular Chemistry, Department of Organic and Macromolecular Chemistry (CMaC), Ghent University, Krijgslaan 281, S4-bis, B-9000, Gent, Belgium.

PMID: 32687137 DOI: 10.1039/d0cp03165h

Abstract

Thermally and photochemically reversible functional groups, such as photodimers of anthracene derivatives, offer interesting stimuli-responsive behaviour. To evaluate their potential for application in reversible polymer networks, accurate kinetic parameters and knowledge of their thermophysical behaviour are required. Accurate kinetic studies of the thermal dissociation of the photodimers in the condensed state, thus without the influence of solvents on their reactivity, is still lacking. A methodology was set up to accurately evaluate the chemical reaction kinetics and complex phase behaviour during the thermal dissociation of photodimers into their corresponding monomers. Temperature-controlled time-resolved FTIR spectroscopy was used to determine the reaction progress, while non-isothermal DSC measurements were used to study the thermophysical changes, resulting from the thermal dissociation reaction. The thermal dissociation behaviour in the condensed state is more challenging than in the solution state due to the crystallinity of the dimers, stabilizing the dimers and thus slowing down the initial dissociation rates. Distinctly different sets of kinetic parameters were found for the dissociation from the molten and the crystalline state. For experiments performed below the melting temperature of the photodimer, the reaction rate changes abruptly as the dimer is partly dissociated and partly dissolved into the formed monomer. This methodology provides an accurate assessment of the reaction kinetics with detailed knowledge about the complex phase behaviour of the mixture of the anthracene photodimer and monomer during thermal dissociation.

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