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Oxidation reactions were preferably investigated to reduction reactions because of the limitations due to the imidazolium cation in the electroactivity windows in the negative region. For example, in classical organic solvent (acetonitrile, dimethylformamide, etc.), the well-known reduction of anthracene exhibits a monoelectronic and reversible electro-chemical process around - 1.89 V/SCE. In alkylimidazolium-based ionic liquids ([BMIM][PF6], [BMIM][NTf2], and [EMIM][NTf2]), we were not able to see the reduction wave of anthracene because the cathodic window limit is narrowed by the reduction of alkylimidazolium ions at -1.8-2 V/SCE.
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2], respectively, under our experimental conditions. The exact values are strongly dependent on the amount of residual water present in the liquid ionic.
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Similar results were obtained in the other investigated ionic liquids
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Similar results were obtained in the other investigated ionic liquids.
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For example through the Stokes-Einstein equation for a spherical molecule D = kT/6πηa, where k is the Boltzmann constan, η the viscosity, and a is the solvodynamic radius of the diffusing species.
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However, to get similar current intensities taking into account the differences in diffusion coefficients, anthracene concentrations in acetonitrile were typically five times lower than that used in the ionic liquids.
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As mentioned in the Experimental Section, a Pt wire coated with polypyrrole is used as a quasireference electrode. We checked this quasireference against the ferrocene/ferricinium couple (E° = 0.405 V/SCE).
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We checked that the concentrations of water were almost the same in all the ionic liquids (less than a factor 2).
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72
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0013342053
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note
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For a comparison between peak currents for the oxidation of the monomer and the reduction of the timer radical cation, one should take into account that the first one corresponds to an exchange of 7 electron per mole against one for the trimer redox couple.
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73
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0013443120
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note
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-1.
-
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74
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0013388895
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note
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diff is expected in low polarity solvent because ω(R) > 0 and has mainly an electrostatic origin.
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