Abstract
Conjugated porous polymers through the emulsion-templating polymerization process are typically prepared as monoliths, and the emulsions are cured via metal-catalyzed cross-coupling reactions. Herein, we report the design and synthesis of well-defined, millimeter-sized conjugated porous polymer beads by combining an oil-in-oil-in-oil (O/O/O) double emulsion as a de novo template and an amino-catalyzed Knoevenagel condensation reaction as a polymerization chemistry to cure such emulsions. The 1,4-phenylenediacetonitrile is reacted with aromatic multialdehydes in the presence of piperidine, and a series of metal-free poly(arylene cyano-vinylene) beads are prepared. All beads exhibit 3D-interconnected microcellular morphology and substantial semiconducting properties, such as strong light harvesting ability in the visible light region with electrochemical band gaps in the range of 2.05-2.33 eV. Finally, the promising photocatalytic activity of these conjugated beads is demonstrated for a model sulfoxidation reaction under visible light irradiation, and near quantitative conversions with excellent chemoselectivities (>99%) are obtained.
Highlights
Conjugated porous polymers through the emulsiontemplating polymerization process are typically prepared as monoliths, and the emulsions are cured via metal-catalyzed cross-coupling reactions
Conjugated polymerized high internal phase emulsions (HIPEs), referred to as “πconjugated polyHIPEs”,6,7 are a unique subclass distinguished from other Conjugated porous polymers (CPPs) by additional porosity on the larger length scale
An important milestone in the design and synthesis of the conjugated polyHIPEs is the possibility of shaping them into well-defined beads or using the organocatalyzed polymerization chemistry for their synthesis
Summary
Conjugated porous polymers through the emulsiontemplating polymerization process are typically prepared as monoliths, and the emulsions are cured via metal-catalyzed cross-coupling reactions. First beaded and metal-free conjugated polyHIPEs are designed by using a combination of the Knoevenagel condensation and a nonaqueous double emulsion system as of the oil-in-oil-in-oil (O/O/O) type.
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