In this letter, we present the synthesis of a new family of -extended dithieno[b,f]phosphepines. The Pd-catalyzed direct-arylation allows the introduction of various substituents, which tune the absorption/emission in the visible range as well as the redox properties. All those modifications were rationalized through DFT calculations. The physical properties of ambipolar phosphepine with diphenylamino substituents conduct us to use it as a semiconductor in a p-type organic field-effect transistors (OFETs).

This article presents the synthesis of a new family of naphthyl‐fused phosphepines through Ni‐mediated C−C coupling. Interestingly, the chlorophosphine oxide intermediate shows strong resistance toward oxidation/hydrolysis owing to a combination of steric hindrance and pnictogen interactions. However, it can undergo substitution reactions under specific conditions. The optical/redox properties and the electronic structure of these new π‐systems were studied experimentally (UV/Vis absorption, emission, cyclic voltammetry) and computationally (TD‐DFT calculations, NICS investigation). Taking advantage of the luminescence of these derivatives, a blue‐emitting OLED has been prepared, highlighting that these novel π‐conjugated P‐heterocycles appear to be promising building blocks for solid‐state lighting applications.

Scheme 2. Synthetic access to 2[OTf]2 and chemical structure of compounds 3-6 2+ (TfOanions have been omitted for clarity)

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