Redox-active, photoluminescent porous polymers based on spirofluorene-bridged -heterotriangulenes and their feasibility as organic cathode materials.

Novel microporous polymers were synthesized through Yamamoto polymerization of selectively brominated spirofluorene-bridged -heterotriangulenes. Extensive characterization, including combustion analysis, ToF-SIMS, IR, and Raman spectroscopy, confirmed the elemental composition and integrity of the polymers. The amorphous polymers, observed by scanning electron microscopy as globular particles aggregating into larger structures, exhibited remarkable thermal stability (decomposition temperatures > 400 °C) and BET surface areas up to 690 m g.

Redox-Active Lewis Pairs Yield Diradicaloids and Enable Modular Control of the Diradical Character.

Stable metal-free diradicaloids are fascinating compounds, typically based on covalent polycyclic or nitrogen-containing π-conjugated frameworks. Unfortunately, their preparation and the modulation of their diradical character require substantial synthetic efforts. The present work introduces a synthetic approach to diradicaloids by the ease and modularity of Lewis pair formation.

Azaarene Dimers.

Binaphthyl-3,3',4,4'-tetraone was prepared and coupled to different bis(TIPS-ethynyl)-substituted (TIPS=triisopropyl silane) aromatic diamines, resulting in the formation of dimeric benzo-fused azaacenes, centrally connected by a single bond. The two halves of the molecules are highly twisted with respect to each other and showed limited electronic interaction in the ground state because their absorption spectra remained very similar to those of the constituting monomers. The dimers displayed greatly reduced fluorescence when compared to the monomers, suggesting that there is a significant interaction of the two azarene units in the excited state.