Functional microporous polymers through Cu-mediated, free-radical polymerization of buckminster [60] fullerene

We report a family of novel microporous polymers constructed through covalent cross linkage of the buckyball and linear dialkyne through Cu-mediated, one-pot synthesis. A novel functionalization-polymerization pathway is described whereby Cu-mediated free radical species, generated in-situ, triggered multiple additions of the ditopic alkyne to C60. The multi-functionalized C60 species act as nodes that afforded microporous networks on extension through proper bridges. Solid-based spectroscopy techniques allowed identification of the chemical composition of the polymers, while gas sorption measurements were utilized to probe the microporosity, surface area, and pore size distribution of the constructed solids. Electron paramagnetic resonance (EPR) spectroscopy demonstrated a free radical pathway for the polymerization reaction. In addition to a relatively unstable diisopropyl nitroxide radical, EPR revealed a quasi-stable, C60-derived, organic radical that exhibits an unusually intense MW absorption and long lifetime at room temperature (>5 days). Two of the reported solids were further investigated and demonstrated activity for electrochemical CO2 reduction. We present here a simple and versatile pathway for using C60 as a building block in the construction of novel materials, and potentially porous magnetic materials encompassing diverse functionality and manipulable properties.

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