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One electron vs. two electron electrochemical and chemical oxidation of electron-donor substituted diketo-pyrrolo-pyrroles
Authors: Luňák Stanislav | Eliáš Zdeněk | Mikysek Tomáš | Vyňuchal Jan | Ludvík Jiří
Year: 2013
Type of publication: článek v odborném periodiku
Name of source: Electrochimica Acta
Publisher name: Pergamon-Elsevier Science Ltd.
Place: Oxford
Page from-to: 351-359
Titles:
Language Name Abstract Keywords
cze Jednoelektronová vs. dvouelektronová elektrochemická a chemická oxidace elektrondonorně substituovaných diketo-pyrrolo-pyrrolů Elektrochemické a chemické (pomocí FeCl3 ) oxidační reakce řady osmi N , N' - dialkylovaných rozpustných diketo-pyrrolo-pyrrolových barviv (DPPS ) substituovaných elektrondonorními a akceptorními substituenty byly zkoumány elektrochemicky a UV - vis spektroskopií a výsledky byly racionalizovány DFT výpočty včetně zkoumání vlivu substituentů na HOMO a LUMO energie, jakož i mechanismus přenosu elektronů. Diketo-pyrrolo-pyrroly; Electrochemie; Absorpční spektra; DFT
eng One electron vs. two electron electrochemical and chemical oxidation of electron-donor substituted diketo-pyrrolo-pyrroles Electrochemical and chemical (using FeCl3) oxidation reactions of a series of eight N,N'-dialkylated soluble diketo-pyrrolo-pyrrole dyes (DPPs) substituted by electron donating and/or electron withdrawing groups were investigated electrochemically and by UV-vis spectrometry and the results were rationalized by DFT calculations. Influence of substituents on HOMO and LUMO energies as well as on the electron transfer mechanism was followed. Destabilization of HOMO by two piperidino-substituents in 3,6-diphenyl-DPP 5 enabled to observe a potential inversion in electrochemical oxidation of this derivative, when a two-electron oxidation occurs leading directly to a dication, whereas other DPPs are oxidized first in a one-electron transfer to a radical cation. In chemical oxidation with FeCl3 the radical cation is produced by two mechanisms: either directly (standard reaction) or in the case of 5 by a comproportionation reaction of neutral molecule and its dication. Using mutual comparison of oxidation potentials and HOMO/LUMO energies a quite realistic limit of FeCl3 oxidation ability in acetonitrile was found. Diketo-pyrrolo-pyrroles; Electrochemistry; Absorption spectra; Potential inversion; TD DFT

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