Alignment and relaxation dynamics of dye molecules in host-guest inclusion compounds as probed by dielectric spectroscopy

Julius Tsuwi, Ricarda Berger, Gaël Labat, Gaëtan Couderc, Norwid Rasmus Behrnd, Phillipp Ottiger, Fabio Cucinotta, Klaus Schürmann, Mariana Bertoni, Lucas Viani, Johannes Gierschner, Jérôme Cornil, Anna Prodi-Schwab, Luisa De Cola, Michael Wübbenhorst, Jürg Hulliger

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Abstract

The alignment and relaxation dynamics of a polar dye molecule, N,N-dimethyl-4(4-nitrophenylazo)aniline (DNAA), in zeolite L and perhydrotriphenylene (PHTP) channels were investigated by means of a combination of optical, dielectric, and quantum-chemical methods. Both the zeolite L and PHTP channels enable the dye molecules to align along the channel axis. An amplified net dipole moment of DNAA in PHTP is observed and attributed to enhanced 1D close alignment of dye molecules. In zeolite L channels, a concentration gradient is found with aggregation at the channel entrances. The dynamics of the dye in zeolite L channels reveals localized conical rotational fluctuation modes following Arrhenius-type activation with energy of 0.31 eV, which we assign to small noninteracting fluctuating polar units of the dyes being loosely aligned or isolated. Unlike zeolite L, relaxations in PHTP are characterized by cooperative wobbling motions interpreted as increased intermolecular dipole interaction due to a closely packed one-dimensional array. Temperature-dependent activation energies of 0.25 eV below 0 °C and 0.37 eV at ambient temperature reflect the role of the soft channel walls in the activation process.

Original languageEnglish (US)
Pages (from-to)6956-6963
Number of pages8
JournalJournal of Physical Chemistry A
Volume114
Issue number26
DOIs
StatePublished - Jul 8 2010

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Tsuwi, J., Berger, R., Labat, G., Couderc, G., Behrnd, N. R., Ottiger, P., Cucinotta, F., Schürmann, K., Bertoni, M., Viani, L., Gierschner, J., Cornil, J., Prodi-Schwab, A., De Cola, L., Wübbenhorst, M., & Hulliger, J. (2010). Alignment and relaxation dynamics of dye molecules in host-guest inclusion compounds as probed by dielectric spectroscopy. Journal of Physical Chemistry A, 114(26), 6956-6963. https://doi.org/10.1021/jp102451w