多孔有机笼配体的合成及催化性能研究

文章通过两步反应简单高效地制备出目标多孔有机笼 RCC3，将其作为配体和 $ CuBr_{2} $ 配位构建多孔有机笼配合物 RCC3@Cu。采用 X-射线衍射（X-ray diffraction，XRD）和电喷雾电离质谱（electrospray ionization mass spectrometry，ESI-MS）表征 RCC3@Cu 的结构与组成，结果表明，RCC3@Cu 配位稳定，有望用于介导原子转移自由基聚合（atom transfer radical polymerization，ATRP）。采用 RCC3 配体介导甲基丙烯酸甲酯（MMA）的 ATRP，2 h 其转化率达到 80%，聚合物分散性指数（polymer dispersity index，PDI）为 1.15；最终转化率为 98.5%，PDI 为 1.16。聚合动力学显示 RCC3 介导的 ATRP 为近似一级反应动力学，符合活性聚合特征。该文研究 RCC3 配体介导不同类型单体的聚合，验证了 RCC3 配体具有单体泛用性。研究结果表明，RCC3 体可有效应用于 ATRP 催化，有进一步研究价值。

In this paper, the target porous organic cages(POCs) RCC3 was simply and efficiently synthesized through a two-step reaction, which was used as a ligand to coordinate with $ CuBr_{2} $ to construct a POCs complex RCC3@Cu. The X-ray diffraction(XRD) and electrospray ionization mass spectrometry(ESI-MS) were used to characterize the structure and composition of RCC3@Cu. It was confirmed that RCC3@Cu was a copper complex with stable coordination structure and was expected to be used to mediate atom transfer radical polymerization(ATRP). RCC3 was employed as a ligand for ATRP of methyl methacrylate(MMA), the conversion rate would achieve up to 80% in 2 h, and the polymer dispersity index(PDI) was 1.15; the final conversion rate could reach 98.5%, and the PDI was 1.16. The polymerization kinetics showed that RCC3-mediated ATRP was approximate to the first-order reaction kinetics, which accorded with the characteristics of living polymerization. Monomer versatility of RCC3 was further demonstrated by the ATRP of various monomers. The results showed that RCC3 ligand can be effectively applied to ATRP catalysis and it is worth further research.