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ESR studies on solvation by using s-butyl trifluoroacetyl nitroxide probe

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Stable s-butyl trifluoroacetyl nitroxide (3) has been generated in electron-transfer reaction of O-benzoyl-N-s-butylhydroxylamine (1) and trifluoroacetyl peroxide (2) in F113 (CFCl2CF2Cl) solution at room temperature. ESR measurement of aN and aHβ values for 3 in 21 solvents has been carried out at 24~ 25°C. The aN values for 3 in 12 aprotic solvents show a linear correlation with the cybotactic solvent parameters ET and Z, i.e. aN = 1.35×10-2 ET+6.84, aN = 0.78×10-2Z+6.88. The physical significance for the slopes, slope × ET or slope × Z, the extrapolated intercepts on the aN axis are linked to the sensitivity of the nitroxide toward the solvation, the magnitude of the overall solvaton effect on the aN values, and the intrinsic aN value of 3 in the ideal gaseous state, respectively. The plots of aN versus noncybotactic solvent constants, such as dipolar moment (μ) and dielectric constant (ε), all show random cases.

10.1163/156856702760129528
/content/journals/10.1163/156856702760129528
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/content/journals/10.1163/156856702760129528
2017-07-22

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