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

Abstract

Novel microporous polymers were synthesized through Yamamoto polymerization of selectively brominated spirofluorene-bridged N-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 m² g⁻¹. Dispersions of the tert-butyl-substituted polymer in different solvents displayed bathochromically shifted emission with remarkable solvatochromism. The polymer is reversibly oxidized at +3.81 V (vs. Li/Li⁺) in composite electrodes with carbon black and reaches specific capacities up to 26 mA h g⁻¹ and excellent cycling stability when implemented as cathode material in lithium-ion batteries. Our results highlight the potential of spirofluorene-bridged N-heterotriangulenes as versatile building blocks for the development of functional redox-active porous polymers.