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Temperature dependence of interactions between stable piperidine-1-yloxyl derivatives and a semicrystalline ionic liquid

  • The stable 2,2,6,6-tetramethylpiperidine-1-yloxyl and its derivatives with hydrogen-bond-forming (-OH, -OSO3H), anionic (-OSO3- bearing K+ or [K(18-crown-6)](+) as counter ion), or cationic (-N+-(CH3)(3) bearing I-, BF4-, PF6- or N- (SO2CF3)(2) as counter ion) substituents are investigated in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide over a wide temperature range. The temperature dependence of the viscosity of the ionic liquid is well described by the Vogel-Fulcher-Tammann equation. Interestingly, the temperature dependence of the rotational correlation time of the spin probes substituted with either a hydrogen-bond-forming group or an ionic substituent can be described using the Stokes-Einstein equation. In contrast, the temperature dependence of the rotational correlation time of the spin probe without an additional substituent at the 4-position to the nitroxyl group does not follow this trend. The activation energy for the mobility of the unsubstituted spin probe, determined from an Arrhenius plot of theThe stable 2,2,6,6-tetramethylpiperidine-1-yloxyl and its derivatives with hydrogen-bond-forming (-OH, -OSO3H), anionic (-OSO3- bearing K+ or [K(18-crown-6)](+) as counter ion), or cationic (-N+-(CH3)(3) bearing I-, BF4-, PF6- or N- (SO2CF3)(2) as counter ion) substituents are investigated in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide over a wide temperature range. The temperature dependence of the viscosity of the ionic liquid is well described by the Vogel-Fulcher-Tammann equation. Interestingly, the temperature dependence of the rotational correlation time of the spin probes substituted with either a hydrogen-bond-forming group or an ionic substituent can be described using the Stokes-Einstein equation. In contrast, the temperature dependence of the rotational correlation time of the spin probe without an additional substituent at the 4-position to the nitroxyl group does not follow this trend. The activation energy for the mobility of the unsubstituted spin probe, determined from an Arrhenius plot of the spin-probe mobility in the ionic liquid above the melting temperature, is comparable with the activation energy for the viscous flow of the ionic liquid, but is higher for spin probes bearing an additional substituent at the 4-position. Quantum chemical calculations of the spin probes using the 6-31G+d method give information about the rotational volume of the spin probes and the spin density at the nitrogen atom of the radical structure as a function of the substituent at the spin probes in the presence and absence of a counter ion. The results of these calculations help in understanding the effect of the additional substituent on the experimentally determined isotropic hyperfine coupling constant.show moreshow less

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Author details:Veronika StrehmelORCiDGND, Hans Rexhausen, Peter StrauchGND, Bernd Strehmer
URL:http://www3.interscience.wiley.com/cgi-bin/jhome/72514732/
DOI:https://doi.org/10.1002/cphc.200900977
ISSN:1439-4235
Publication type:Article
Language:English
Year of first publication:2010
Publication year:2010
Release date:2017/03/25
Source:Chemphyschem. - ISSN 1439-4235. - 11 (2010), 10, S. 2182 - 2190
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie
Peer review:Referiert
Publishing method:Open Access
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