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A family of cyclic phosphine‐disiloxane featuring peri‐substituted naphthyl(Nap)/acenaphthyl(Ace) scaffolds has been prepared and fully characterized including X‐ray structure, which enables a detailed structural analysis. This straightforward synthesis takes advantage of both ortho‐ and peri‐substitution of Nap/Ace‐substituted phosphine oxides. The synthetic method allows diversifying the polycyclic aromatic platform (Nap and Ace) as well as the Si substituents (Me and Ph). Despite a strong steric congestion, the P‐atom remains reactive toward oxidation or coordination. In particular, Au(I) complex could be prepared. All the compounds display absorption/luminescence in the UV‐Vis range. Surprisingly, the P‐trivalent derivatives display unexpected luminescence in the green in solid‐state. [ABSTRACT FROM AUTHOR]

We report the straightforward synthesis of unprecedented electron‐acceptors based on dicationic P‐containing PAHs (Polycyclic Aromatic Hydrocarbons) based on copper mediated radical approach. In these systems, two phosphoniums are connected through various PAHs backbones. The impact of π‐extension on both the optical and redox properties is investigated using a joint experimental (UV/Vis absorption, fluorescence and cyclic voltammetry) and theoretical approach (TD‐DFT calculations). Finally, (spectro)‐electrochemical studies prove that these compounds possess three redox states and EPR studies confirm the in situ formation of an organic radical delocalized on the PAH backbone. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]