Abstract
A flexible long-chain nitroxide biradical of the structure R6–(CH2)2OOC–(CH2)8–COO–(CH2)2–R6, 1, where –R6 is the 1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl residue, has been investigated by X-band electron paramagnetic resonance spectroscopy in CH3CN solutions at variable temperature and pressure. The effect of changes of the solution viscosity on the intramolecular electron spin exchange in 1 has been characterized in terms of dynamic and thermodynamic parameters such as the equilibrium constant describing the transition of the elongated and coiled effective configuration, τc/τ, and the characteristic spin-exchange time τeff and its associated Arrhenius activation energy. It was revealed that the intramolecular dynamics in 1 do not follow the Debye-Stokes–Einstein law.
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