We report the efficient synthesis of electron-acceptors based on cationic P-doped polycyclic aromatic hydrocarbons. In particular, exo-skeletal modifications of the π-core were performed and their effect on the optical and redox properties was studied and compared to the effect of endo-skeletal modifications. Combined experimental (spectroelectrochemical and electron paramagnetic resonance) and theoretical studies performed on this entire family provide in-depth characterization of the reduced species and specifically of the stable radical cations formed and afford a guideline for the property tuning of such derivatives. Finally, electrochemical modulation of fluorescence performed on two compounds highlights the potential of these intrinsically switchable electroactive fluorophores.