Redox Active cAAC-Fluorene/Indene Systems Displaying Solvatochromism, Green Luminescence and pH Sensing: Functionalization of Fluorenyl/Indenyl Rings with Radical Carbene.

ABSTRACT

Two new series of air stable compounds of cAACX = fluorene/indene (X = Me2 , Et2 , Cy) [cAAC = cyclic (alkyl) amino carbene] have been isolated and well characterized by X-ray single crystal diffraction, photoluminescence, cyclic voltammogram (CV) and electron paramagnetic resonance (EPR) studies. Fluorescence studies reveals green light emission of cAAC bonded fluorene, whereas free fluorene generally displays a violet emission. Interestingly, the sterically crowded cAAC-fluorene analogue display solvatochromism and CF3 CO2 H sensing in solution. CV of the these compounds show a quasi-reversible electron transfer process, indicating the functionalization of fluorene/indene with radical anionic form of carbene, confirmed by CV/EPR measurements. DFT/TDDFT calculations and energy decomposition analysis coupled with natural orbital for chemical valence (EDA-NOCV) have been carried out to study different aspects of bonding and electronic transitions. Such a class of redox active and thermally stable organic molecules may be suitable for molecule based spin memory devices in future.