Di- vs. tetra-substituted quinonediimines: a drastic effect on coordination chemistry.
Fiche publication
Date publication
octobre 2017
Journal
Dalton transactions (Cambridge, England : 2003)
Auteurs
Membres identifiés du Cancéropôle Est :
Dr ELHABIRI Mourad
Tous les auteurs :
Lavaud L, Chen Z, Elhabiri M, Jacquemin D, Canard G, Siri O
Lien Pubmed
Résumé
We describe the first isolation of N,N'-disubstituted benzoquinonediimines (QDIs) 2 which revealed drastically different properties compared to N,N',N'',N'''-tetrasubstituted QDIs 1 due to the absence of N-substituents in the "upper part" of the molecule. Three major differences could be highlighted thanks to the present joint experimental and theoretical investigation: (1) the metalation with different metal precursors revealed a specific behaviour in coordination chemistry giving access to novel complexes with unprecedented stoichiometry and remarkable absorption properties. More specifically, a new monoplatinum complex that is able to absorb light from the UV up to the NIR region because of its unique delocalization pathway across the metal centre was obtained; (2) this new class of di-substituted QDIs showed an exceptionally broad pK range (ΔpK∼ 8) that could be explained by the possible tuning of the basicity of each imine which is now attainable; (3) these quinones could be used as reagents in organic synthesis to form the previously unknown N,N',N'',N'''-tetrasubstituted QDIs with tuneable substituents (aryl vs. alkyl), previously unknown, as a new ligand for coordination chemistry.
Référence
Dalton Trans. 2017 Oct 14;46(38):12794-12803