Conjugated microporous polymers (CMPs) are porous organic materials that display (semi)conducting behavior due to their highly π-conjugated structures. As such, they are promising next-generation materials for applications requiring both conductivity and porosity, such as supercapacitive energy storage and electrochemical sensing. However, most CMPs and related porous aromatic frameworks (PAFs) are currently prepared using expensive transition metal-based catalysts under solvothermal conditions, significantly increasing their manufacturing costs. Herein, we demonstrate that the ionothermal cyclotrimerization of methyl ketones via the aldol reaction represents a new strategy for the solvent-free synthesis of CMPs and PAFs. Specifically, we show that 1,3,5-triacetylbenzene and tetrakis(4-acetylphenyl)methane can be polymerized in molten zinc chloride to produce highly conjugated and microporous materials, as confirmed by 77 K N₂ adsorption measurements in conjunction with UV–vis, Raman, and solid-state NMR spectroscopies. The CMP prepared from 1,3,5-triacetylbenzene demonstrates higher charge storage capacities (up to 172 F/g) than a commercially available supercapacitor carbon, reflecting the promise of cyclotrimerized CMPs for electrical energy storage applications.

中文翻译：

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甲基酮无溶剂电离热环三聚共轭微孔聚合物

共轭微孔聚合物 (CMP) 是多孔有机材料，由于其高度 π 共轭结构而显示出（半）导电行为。因此，它们是有前途的下一代材料，可用于需要导电性和孔隙率的应用，例如超级电容储能和电化学传感。然而，目前大多数 CMP 和相关的多孔芳香骨架 (PAF) 是在溶剂热条件下使用昂贵的过渡金属基催化剂制备的，这显着增加了它们的制造成本。在此，我们证明了通过羟醛反应进行甲基酮的离子热环三聚反应代表了一种无溶剂合成 CMP 和 PAF 的新策略。具体来说，我们表明 1,3,₂吸附测量与 UV-vis、拉曼和固态 NMR 光谱相结合。由 1,3,5-三乙酰苯制备的 CMP 表现出比市售超级电容器碳更高的电荷存储容量（高达 172 F/g），反映了环三聚 CMP 在电能存储应用中的前景。