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Laserflash‐photolysis of the p ‐Chloranil/naphthalene system: Characterization of the naphthalene radical cation in a fluid medium ,
Author(s) -
Gschwind Rudolf,
Haselbach Edwin
Publication year - 1979
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19790620404
Subject(s) - chemistry , chloranil , electron transfer , naphthalene , dissociation (chemistry) , ion , quenching (fluorescence) , ionic bonding , analytical chemistry (journal) , reaction rate constant , photodissociation , fluorescence , photochemistry , kinetics , chromatography , physics , organic chemistry , quantum mechanics
Excitation of p ‐Chloranil ( CA ) in propylcyanide (PrCN) at room temperature leads to rapid production of 3 CA * which decays predominantly to CA H· with k d 0= 1.6 · 10 5 s −1 . Observation of a photoinduced current suggests simultaneous production of CA − formed by electron transfer quenching of 3 CA * by the medium. Added naphthalene ( NP ) quenches 3 CA * with k q = 7.0 · 10 9 M −1 S −1 ; NP + is unambigously identified as product (besides CA − ) of the electron transfer process. Dissociation of the ion pair occurs with essentially unit probability. Higher concentrations of NP lead to the formation of ( NP ) + 2 . Pertinent spectroscopic parameters established for NP + under the conditions used are λ max = 685 nm (ϵ = 2970) using the known parameters of CA \documentclass{article}\pagestyle{empty}\begin{document}$ 1^{+ \atop \dot{}} $\end{document} as reference. NP + and CA \documentclass{article}\pagestyle{empty}\begin{document}$ 1^{+ \atop \dot{}} $\end{document} decay by charge annihilation with k r = 4.5 · 10 9 M −1 S −1 . The deviation from the diffusion controlled rate constant expected for ionic species, is discussed in view of the spin characteristics of the process. Comparison with two other ion recombination reactions leads to the conclusion that ‘inverted behaviour’ as expected from Marcus ' theory does also not show up for backward e − ‐transfer between two ions (produced by forward e − ‐transfer between two neutrals). Residual absorptions in the system are ascribed to CA H·, tentatively proposed to originate from H + ‐abstraction by CA \documentclass{article}\pagestyle{empty}\begin{document}$ 1^{+ \atop \dot{}} $\end{document} from the solvent. NP + appears to be a rather stable species with respect to the medium if the latter is meticulously purified.