To tackle this challenge, we here take advantage of the possibility to convert a cationic  4 , -P + into a neutral  4 , 5 -P (Scheme 1) to afford multi-stage redox systems based on organophosphorus derivatives. Indeed we report the general and straightforward synthesis of an unprecedented family of dicationic P-containing Polycyclic Aromatic Hydrocarbons (PAHs) 2-6[OTf]2 where two  4 , 4 -P + are connected through various -backbones. The impact of extension on both optical and redox properties is investigated using a joint experimental/theoretical approach. Finally, (spectro)-electrochemical studies prove that these compounds possess three redox states and EPR studies confirms the in situ formation of radicals demonstrating that these novel acceptors behave as "viologenlike" redox systems. To prepare the targeted bisphosphoniums, we rely on a copper mediated radical approach. This method was recently used to prepare -conjugated phosphoniums. 12 In our hands, the double phosphacyclization of bisphosphane 1 cleanly afforded 1,8-bisphosphapyrenium 2[OTf]2 (87% yield, Scheme 2), as an air and moisture stable derivatives characterized by a single peak in 31 P NMR ( = + 1.3 ppm). This compound was fully characterized by multinuclear NMR, high resolution mass spectrometry and X-ray diffraction (vide infra). In addition, 2[OTf]2 is soluble in classical organic solvents. To illustrate the versatility of this molecular engineering strategy, various polyaromatic diphosphanes were converted into their dicationic analogs 3-6[OTf]2 in good yields (Scheme 2). This allowed us to prepare a novel family of dicationic P-containing PAHs featuring variable -cores. They all display two cationic  4  4 -P centers connected through a bridge featuring an even number of sp 2 C-atoms.