Intramolecular Mobility in Nitroxide Biradicals with Flexible Linkers

Applied Magnetic Resonance - Tập 51 - Trang 1031-1040 - 2020
Günter Grampp1, Van Anh Tran2, Petr V. Pantyukhov3, Alexander I. Kokorin3,4
1Institute of Physical and Theoretical Chemistry, Graz University of Technology, Graz, Austria
2School of Chemical Engineering, Hanoi University of Science and Technology, Hanoi, Vietnam
3Plekhanov Russian University of Economics, Moscow, Russian Federation
4N.N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, Moscow, Russian Federation

Tóm tắt

Intramolecular electron spin exchange has been studied by X-band electron paramagnetic resonance (EPR) spectroscopy in two long-chain flexible nitroxide biradicals existing in fluid solutions in three spectroscopy-different spatial conformations as a function of temperature, solvent viscosity and polarity. Certain thermodynamic parameters of the conformational transitions were calculated from the EPR spectra. The process of spin-exchange in these biradicals dissolved in five different alcohols was compared with that in the non-polar solvents (toluene) and aprotic (acetonitrile), as well as with two other biradicals studied earlier, and with thermodynamic characteristics of the solvents. A distinct correlation was found between macroscopic (solvent viscosity) characteristics of solvents and thermodynamic parameters of the intramolecular conformational transitions.

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