To prepare our family of λ 5 -phosphinine dimers, we relied on the molecular engineering of DCNP, which is a highly stable ylidic fluorophore with great synthetic versatility. Our first approach is based on cross-coupling reactions starting from bromo-DCNP 1a (Scheme 1). To prepare the dimers linked through various π-bridges, 1a was subjected to Pd-catalysed cross-coupling with the corresponding dioxaborolane to afford dimers 2-4 in moderate to excellent yields (Scheme 1). Compound 5, bridged by an alkyne, was prepared in moderate yields according to an iterative sequence of Sonogashira coupling and deprotection (Scheme 1). Scheme 1: Synthesis of π-extended λ 5 -phosphinine dimers 2-5