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- W2024552431 abstract "Three bis(2-tert-butyl-2,3-diazabicyclo[2.2.2]oct-3-yl) radical cation salts, bridged by 2,3,5,6-tetramethylbenzene-1,4-diyl (1+PF6-), biphenylene-4,4‘-diyl (2+PF6-), and 9,9-dimethyl-fluorene-2,7-diyl (3+NO3-) groups, have been studied in methylene chloride. The transition energy at band maximum (Eop) increases as concentration increases and when nBu4+BF6- is added, indicating that ion pairing increases Eop. The Eop data fit a simple ion pairing equilibrium, giving ion pairing equilibrium constants at 293 K of 3100, 3100, and 6100 M-1, respectively. Electron-transfer rate constants measured by ESR are reported for 0.19 mM 2+PF6- and for 1 mM 2+PF6- and 3+NO3- in the presence of 20 mM nBu4+BF6- in methylene chloride. Prediction of kET from the optical spectrum of 2+PF6- containing excess nBu4+BF6- was made both assuming the optical ET is endoenthalpic by an amount calculated from the increase in Eop, and that ΔG° = 0 (that is, that the ion pairing effect may be lumped into the electron transfer coordinate along with the vertical and solvent reorganization effects). The predicted rate constant for the latter is only a factor of 2.5 times larger the former, so both agree rather well with the ESR-derived rate constant." @default.
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- W2024552431 date "1999-06-19" @default.
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- W2024552431 title "Ion Pairing Effects on Bis(Hydrazine) Intervalence Radical Cations" @default.
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- W2024552431 doi "https://doi.org/10.1021/jp991294h" @default.
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