Free radical studies by resonance Raman spectroscopy: Chemically and photochemically generated 1,4‐diaminobenzene radical cation

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<jats:title>Abstract</jats:title><jats:p>The free radical cation of 1,4‐diaminobenzene (<jats:italic>p</jats:italic>‐phenylenediamine, PPD<jats:sup>+.</jats:sup>) has been generated in aqueous solution, wherein it is short‐lived, by oxidation of the parent compound with bromine. The same PPD<jats:sup>+.</jats:sup> radical has also been produced by UV photolysis of the parent at 77 K in an ethanolic glassy matrix. Resonance Raman spectra of the radical and its parent are reported and analysed in detail with the aid of normal coordinate and molecular orbital calculations. Evidence is presented for (PPD<jats:sup>+.</jats:sup>)<jats:sub>2</jats:sub> dimer formation in aqueous solution at room temperature.</jats:p>

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