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Customizing Photoredox Properties of PXX‐based Dyes through Energy Level Rigid Shifts of Frontier Molecular Orbitals
Author(s) -
Sciutto Andrea,
Fermi Andrea,
Folli Andrea,
Battisti Tommaso,
Beames Joseph M.,
Murphy Damien M.,
Bonifazi Davide
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201705620
Subject(s) - oxidizing agent , chromophore , atomic orbital , chemistry , excited state , photochemistry , molecule , imide , halogenation , substrate (aquarium) , molecular orbital , halide , solvent , combinatorial chemistry , electron , organic chemistry , physics , oceanography , quantum mechanics , nuclear physics , geology
Here we describe the synthesis of electron‐rich PXX derivatives in which the energy levels of the excited states have been rigidly shifted through the insertion of imide groups. This has allowed the development of a new series of oxygen‐doped photoredox‐active chromophores with improved oxidizing and reducing properties. Capitalizing on the dehalogenation of organic halides as a model reaction, we could investigate the photooxidative and photoreductive potential of these molecules in model chemical transformations. Depending on the substrate, solvent and dye the reaction mechanism can follow different paths. This prompted us to consider the first chemoselective transformation protocol, in which two different C−Br bonds could be chemoselectively reacted through the sequential photoactivation of two different colorants.