Chemical transformations of push-pull fluorenones: Push-pull dibenzodicyanofulvenes as well as fluorenone- And dibenzodicyanofulvene-tetracyanobutadiene conjugates

Push-pull fluorenones (FOs) were synthesized by treating a benzopentalenequinone (BPO) derivative with alkynes that bear an electron-rich aniline moietyviaa regioselective [4 + 2] cycloaddition (CA) followed by a [4 + 1] retrocycloaddition (RCA). The resulting FOs were readily converted into dibenzodicyanofulvenes (DBDCFs) by treatment with malononitrile in the presence of TiCl₄and pyridine. The FOs and DBDCFs exhibit intramolecular charge-transfer (ICT) that manifests in absorptions at 350-650 nm and amphoteric electrochemical behavior. Furthermore, FOs and DBDCFs that contain a C-C bond react with tetracyanoethylene in a formal [2 + 2] CA followed by a retro-electrocyclization to afford sterically congested tetracyanobutadiene (TCBD) conjugates. The substituent (H or Me) on the aromatic ring adjacent to the butadiene moiety thereby determines whether the butadiene adopts an s-cisor s-transconformation, and thus controls the physicochemical properties of the resulting TCBDs. The TCBD conjugates exhibit ICT absorptions (≤800 nm) together with up to four reversible reduction steps.