We thus decided to prepare λ 5 -phosphinine dimers based on the DCNP scaffold (see target B, Fig. ) to develop fluorescent multi-stage electron donors. In this article, we report the straightforward synthesis of an unprecedented family (2-6, Schemes 1 and 2) where two ylidic P atoms are connected through various π-backbones featuring an even number of sp 2 carbons. The impact of the bridge on both the optical (absorption/emission) and redox properties, and in particular the presence of three redox states, is investigated using a joint experimental/theoretical approach. Finally, electrofluorochromic study was used to prove that these λ 5 -phosphinine dimers behave as intrinsically switchable electroactive fluorophores and can be used for their redox properties, in addition to their recognized potential for luminescence.