SET and HAT/PCET acid-mediated oxidation processes in helical shaped fused bis-phenothiazines |
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Authors: | Prof Riccardo Amorati Prof Luca Valgimigli Dr Andrea Baschieri Dr Yafang Guo Dr Fabio Mollica Prof Stefano Menichetti Michela Lupi Dr Caterina Viglianisi |
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Institution: | 1. Department of Chemistry “G. Ciamician”, University of Bologna, Via S. Giacomo 11, 40126 Bologna, Italy;2. Department of Chemistry “U. Schiff”, University of Florence, Via Della Lastruccia 3–13, Sesto Fiorentino, 50019 Firenze, Italy |
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Abstract: | Helical shaped fused bis-phenothiazines 1 – 9 have been prepared and their red-ox behaviour quantitatively studied. Helicene radical cations (Hel.+) can be obtained either by UV-irradiation in the presence of PhCl or by chemical oxidation. The latter process is extremely sensitive to the presence of acids in the medium with molecular oxygen becoming a good single electron transfer (SET) oxidant. The reaction of hydroxy substituted helicenes 5 – 9 with peroxyl radicals (ROO.) occurs with a ‘classical’ HAT process giving HelO. radicals with kinetics depending upon the substitution pattern of the aromatic rings. In the presence of acetic acid, a fast medium-promoted proton-coupled electron transfer (PCET) process takes place with formation of HelO. radicals possibly also via a helicene radical cation intermediate. Remarkably, also helicenes 1 – 4 , lacking phenoxyl groups, in the presence of acetic acid react with peroxyl radicals through a medium-promoted PCET mechanism with formation of the radical cations Hel.+. Along with the synthesis, EPR studies of radicals and radical cations, BDE of Hel-OH group (BDEOH), and kinetic constants (kinh) of the reactions with ROO. species of helicenes 1 – 9 have been measured and calculated to afford a complete rationalization of the redox behaviour of these appealing chiral compounds. |
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Keywords: | helicene radical helicene radical cation HAT PCET SET |
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