Naphthyl-Fused Phosphepines: Luminescent Contorted Polycyclic P-Heterocycles

Abstract

This article presents the synthesiso fanew family of naphthyl-fused phosphepines through Ni-mediated CÀC coupling. Interestingly,t he chlorophosphine oxide intermediate shows strong resistance toward oxidation/hydrolysis owing to ac ombination of steric hindrance and pnictogen interactions. However,i tc an undergo substitution reactions under specific conditions. The optical/redox properties and the electronic structureo ft hese new p-systems were stud-ied experimentally (UV/Vis absorption, emission, cyclic voltammetry) and computationally (TD-DFT calculations, NICS investigation). Ta king advantage of the luminescence of these derivatives, ab lue-emittingO LED hasb een prepared, highlighting that these novel p-conjugated P-heterocycles appear to be promising buildingb locks for solid-state lighting applications.[a] T.[**] Ap revious versiono ft his manuscripth as been deposited on ap reprint server (https://doi.org/10.26434/chemrxiv.9892001.v1).Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.

Taking Advantage of Ortho- and Peri-Substitution to Design Original 9-Membered P,O,Si-Heterocycles

“…During our study of the reactivity of (8-bromonaphthalen-1-yl)diphenylphosphine oxide (Scheme 1), 8 we observed that the lithiation of 1 followed by quenching with chlorodimethylsilane does not lead to the expected peri-substituted silane-phosphine oxide but to a peri-substituted Nap featuring a nine membered ring incorporating a phosphine and a disiloxane bridge (Compound 3, Scheme 1). This unexpected compound was unambiguously characterized by multinuclear NMR, mass spectrometry and X-ray diffraction (Scheme 1, for full X-ray diffraction study and comparison, see below).…”