Herein, an approach via combination of confined porous textures and reversible deactivation radical polymerization techniques is proposed to advance synthetic polymer chemistry, i.e., a connection of metal–organic frameworks (MOFs) and activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP). Zn₂(benzene-1,4-dicarboxylate)₂(1,4-diazabicyclo[2.2.2]octane) [Zn₂(bdc)₂(dabco)] is utilized as a reaction environment for polymerization of various methacrylate monomers (methyl, ethyl, benzyl, and isobornyl methacrylate) in a confined nanochannel, resulting in polymers with control over dispersity, end functionalities, and tacticity with respect to distinct molecular size. To refine and reconsolidate the compartmentation effect on polymer regularity, initiator-functionalized Zn MOF was synthesized via cocrystallization with an initiator-functionalized ligand, 2-(2-bromo-2-methylpropanamido)-1,4-benzenedicarboxylate (Brbdc), in different ratios (10%, 20%, and 50%). Through the embedded initiator, surface-initiated ARGET ATRP was directly initiated from the walls of the nanochannels. The obtained polymers had a high molecular weight up to 392 000. Moreover, a significant improvement in end-group functionality and stereocontrol was observed, entailing polymers with obvious increments in isotacticity. The results highlight a combination of MOFs and ATRP that is a promising and universal methodology to prepare various polymers with high molecular weight exhibiting well-defined uniformity in chain length and microstructure as well as the preserved chain-end functionality.

中文翻译：

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寻求自由基聚合的最终控制：功能化的金属有机骨架是金属催化聚合的强大环境

在此，提出了一种通过结合受限的多孔织构和可逆的失活自由基聚合技术来提高合成聚合物化学的方法，即金属有机骨架（MOF）与通过电子转移原子转移自由基聚合（ARGET ATRP）再生的活化剂的连接。Zn ₂（苯-1,4-二羧酸酯）₂（1,4-二氮杂双环[2.2.2]辛烷）[Zn ₂（bdc）₂[（dabco）]用作在封闭的纳米通道中聚合各种甲基丙烯酸酯单体（甲基，乙基，苄基和甲基丙烯酸异冰片酯）的反应环境，从而可以控制聚合物的分散性，末端官能度和相对于不同分子的立构规整度尺寸。为了改善和巩固对聚合物规则性的分隔作用，通过与引发剂官能化的配体2-（2-溴-2-甲基丙酰胺基）-1,4-苯二甲酸（Brbdc）共结晶，合成了引发剂官能化的Zn MOF。比率（10％，20％和50％）。通过嵌入式引发剂，表面引发的ARGET ATRP是直接从纳米通道壁引发的。所获得的聚合物具有高达392 000的高分子量。此外，观察到在端基官能团和立体控制方面的显着改善，这导致聚合物的全同立构规整度明显增加。结果表明，MOF和ATRP的组合是一种有前途的通用方法，可用于制备高分子量的各种聚合物，这些聚合物在链长和微结构上均具有明确定义的均匀性，并保留了链端官能度。