ChemElectroChem
ChemElectroChem
5 years ago

Redox Properties and Interchromophoric Electronic Interactions in Isoalloxazine−Anthraquinone Dyads

Redox Properties and Interchromophoric Electronic Interactions in Isoalloxazine−Anthraquinone Dyads
M. Ángeles Farrán, Giovanni Valenti, Gianluca Accorsi, Rosa María Claramunt, Francesco Paolucci, Massimo Marcaccio, Matteo Iurlo
The electrochemistry of a family of recently synthesized isoalloxazine cyclophanes containing anthraquinones, variously substituted and linked by aliphatic chains of different lengths, has been studied. The redox behavior of such species was elucidated by complementing the voltammetric studies with DFT molecular modelling. In these cyclophanes (mimicking the active centers of enzymes), the distance between chromophores and their reciprocal orientations were found to significantly modify their redox properties. Inter-moiety π−π stacking plays an important role in the electrochemical behavior by modulating the orbital energies, which leads to an inversion of the localization of the first reduction, with the anthraquinone being reduced before the more electron-accepting flavine. Family affairs: Electrochemical investigation of a family of isoalloxazine−anthraquinone cyclophanes, assisted by DFT modelling, indicates that the interchromophoric distance and orientation of the units affect the π−π stacking, thus leading to the modulation of the orbital energies to give an inversion of the localization for the first reduction process.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/celc.201701374

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