Kautny2017.pdf (4.87 MB)

Charge-transfer states in triazole linked donor-acceptor materials: Strong effects of chemical modification and solvation

Download (4.87 MB)
journal contribution
posted on 06.03.2018, 10:42 by Paul Kautny, Florian Glocklhofer, Thomas Kader, Jan-Michael Mewes, Berthold Stoger, Johannes Frohlich, Daniel Lumpi, Felix Plasser
© the Owner Societies 2017. A series of 1,2,3-triazole linked donor-acceptor chromophores are prepared by Click Chemistry from ene-yne starting materials. The effects of three distinct chemical variations are investigated: enhancing the acceptor strength through oxidation of the sulphur atom, alteration of the double bond configuration, and variation of the triazole substitution pattern. A detailed photophysical characterization shows that these alterations have a negligible effect on the absorption while dramatically altering the emission wavelengths. In addition, strong solvatochromism is found leading to significant red shifts in the case of polar solvents. The experimental findings are rationalized and related to the electronic structure properties of the chromophores by time-dependent density functional theory as well as the ab initio algebraic diagrammatic construction method for the polarization propagator in connection with a new formalism allowing to model the influence of solvation onto long-lived excited states and their emission energies. These calculations highlight the varying degree of intramolecular charge transfer character present for the different molecules and show that the amount of charge transfer is strongly modulated by the conducted chemical modifications, by the solvation of the chromophores, and by the structural relaxation in the excited state. It is, furthermore, shown that enhanced charge separation, as induced by chemical modification or solvation, reduces the singlet-triplet gaps and that two of the investigated molecules possess sufficiently low gaps to be considered as candidates for thermally activated delayed fluorescence.

Funding

This work was supported by the TU Wien research funds and by the VSC Research Center funded by the Austrian Federal Ministry of Science, Research and Economy (bmwfw). JMM gratefully acknowledges funding from the Alexander von Humboldt Foundation.

History

School

  • Science

Department

  • Chemistry

Published in

Physical Chemistry Chemical Physics

Volume

19

Issue

27

Pages

18055 - 18067

Citation

KAUTNY, P. ...et al., 2017. Charge-transfer states in triazole linked donor-acceptor materials: Strong effects of chemical modification and solvation. Physical Chemistry Chemical Physics, 19(27), pp. 18055-18067.

Publisher

© the Owner Societies 2017. Published by Royal Society of Chemistry

Version

VoR (Version of Record)

Publisher statement

This work is made available according to the conditions of the Creative Commons Attribution 3.0 Unported (CC BY 3.0) licence. Full details of this licence are available at: http://creativecommons.org/licenses/by/3.0/

Acceptance date

25/06/2017

Publication date

2017

Notes

This is an Open Access Article. It is published by Royal Society of Chemistry under the Creative Commons Attribution 3.0 Unported Licence (CC BY). Full details of this licence are available at: http://creativecommons.org/licenses/by/3.0/

ISSN

1463-9076

Language

en

Licence

Exports

Loughborough Publications

Keywords

Licence

Exports