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With the exception of toluene, the oxidation potentials for the alkylbenzenes used to calculated the reaction exothermicities were taken from ref 8a. The oxidation potential of toluene was estimated to be 2.33 V versus SCE based on measurements in trifluoroacetic acid.12b,c In trifluoroacetic acid, the reported oxidation potentials of the other alkylbenzenes, when referenced versus SCE, are on average ∼0.02 V higher than those in ref 8a
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12b,c In trifluoroacetic acid, the reported oxidation potentials of the other alkylbenzenes, when referenced versus SCE, are on average ∼0.02 V higher than those in ref 8a.
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48
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The negatively charged counterion may contribute to stabilization in less polar solvents than acetonitrile where ion pairing may be significant. 13b
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The rate constants for quenching of some excited pyrylium salts were also reported by Jacques et al.6d
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For more detailed discussions of the analysis of the bandwidths of such exciplex spectra, the derivation of reduced spectra from measured spectra, and the determination of ion pair energies from such spectra, see ref 11e. The similarity in the reorganization energies for these systems contrasts with that found for corresponding emissions of the smaller electron acceptor tetracyanobenzene with various alkylbenzene donors, where a decrease in reorganization energy with increasing substitution (and thus size) of the donor could be detected.11e
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For comparison, the C-N bond dissociation energies of the N-methylpyridinium and N-cyanomethylpyridinium cations calculated at the B3LYP/6-31G* level of theory are 111 and 84 kcal/mol, respectively.
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For comparison, the C-N bond dissociation energies of the N-methylpyridinium and N-cyanomethylpyridinium cations calculated at the B3LYP/6-31G* level of theory are 111 and 84 kcal/mol, respectively.
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