Herein, we built a two-fold interpenetrated, robust pillar-bilayered framework from anionic [Cd3(µ2-OH)(COO)6] unit and –NH2 hooked nitrogen-rich struts. The activated MOF shows temperature variable CO2 adsorption with minimum uptake loss during multiple cycle and under humid environment. Interestingly, CO2/N2 selectivity displays notable enhancement upon rise in temperature, reaching a value of 490 at 313 K that outperforms some best-performing adsorbents. The MOF catalyses solvent-free and mild-condition CO2 cycloaddition with wide substrate scope, good recyclability and high turnover number. Opposed to common Lewis acid-mediated reaction, pendent –NH2 sites activate the epoxide via H-bonding interaction, as validated from performance comparison of an un-functionalized MOF, and guest-mediated concomitant fluorescence articulation. These hydrogen-bond-donating (HBD) sites further benefit effective Friedel−Crafts (FC) alkylation of indole with β-nitrostyrene, where product is additionally characterized by single-crystal X-ray diffraction. The reaction includes twenty electronically assorted substrates and transpires with high catalyst reusability. The key role of HBD moiety in directing C-C coupling is detailed from correlating the performance of two isostructural MOFs without –NH2 site, judicious choice of the substrates, and fluorescence modification derived framework-electrophile interaction. Importantly, pore-space-partitioning by flanked pyridyl linker induces size-selectivity via restricting the channel diffusion of sterically encumbered indole.

中文翻译：

---

富氮离子金属有机容器：温度触发改进的 CO2 分离和氢键介导的环加成反应，孔隙空间分配诱导尺寸选择性 Friedel-Crafts 烷基化


在此，我们从阴离子 [Cd3（μ2-OH）（COO）6] 单元和 –NH2 钩状富氮支柱构建了一个双重互穿、坚固的柱双层框架。活化的 MOF 显示温度可变的 CO2 吸附，在多个循环和潮湿环境中具有最小的吸收损失。有趣的是，CO2/N2 选择性在温度升高时表现出显着增强，在 313 K 时达到 490 的值，优于一些性能最好的吸附剂。MOF 催化无溶剂和温和条件的 CO2 环加成反应，具有广泛的底物范围、良好的可回收性和高周转率。与常见的 Lewis 酸介导的反应相反，下垂的 -NH2 位点通过 H 键相互作用激活环氧化物，这从非功能化 MOF 的性能比较和客体介导的伴随荧光接合中得到验证。这些氢键供体 （HBD） 位点进一步有利于吲哚与 β-硝基苯乙烯的有效 Friedel-Crafts （FC） 烷基化反应，其中产物还以单晶 X 射线衍射为特征。该反应包括 20 种电子分类底物和蒸腾物，催化剂可重复使用性高。HBD 部分在指导 C-C 偶联中的关键作用通过关联两个没有 –NH2 位点的同构 MOF 的性能、底物的明智选择以及荧光修饰衍生的框架-亲电相互作用来详细说明。重要的是，侧翼吡啶基接头的孔隙空间分配通过限制空间位阻吲哚的通道扩散来诱导尺寸选择性。