The rational design and synthesis of robust metal–organic frameworks (MOFs) based on novel organic building blocks are fundamental aspects of reticular chemistry. Beyond simply fabricating new organic linkers, however, it is important to elucidate structure–property relationships at the molecular level to develop high-performing materials. In this work, we successfully targeted a highly porous and robust cage-type MOF (NU-200) with an nbo-derived fof topology through the deliberate assembly of a cyclohexane-functionalized iron­(II)-clathrochelate-based meta-benzenedicarboxylate linker with a Cu2(CO2)4 secondary building unit (SBU). NU-200 exhibited an outstanding adsorption capacity of xenon and a high ideal adsorbed solution theory (IAST) predicted selectivity for a 20/80 v/v mixture of xenon (Xe)/krypton (Kr) at 298 K and 1.0 bar. Our extensive computational simulations with grand canonical Monte Carlo (GCMC) and density functional theory (DFT) on NU-200 indicated that the MOF’s hierarchical bowl-shaped nanopockets surrounded by custom-designed cyclohexyl groupsinstead of the conventionally believed open metal sites (OMSs)played a crucial role in reinforcing Xe-binding affinity. The optimally sized pockets firmly trapped Xe through numerous supramolecular interactions including Xe···H, Xe···O, and Xe···π. Additionally, we validated the unique pocket confinement effect by experimentally and computationally employing the similarly sized probe, sulfur dioxide (SO2), which provided significant insights into the molecular underpinnings of the high uptake of SO2 (11.7 mmol g–1), especially at a low pressure of 0.1 bar (8.5 mmol g–1). This work therefore can facilitate the judicious design of organic building blocks, producing MOFs featuring tailor-made pockets to boost gas adsorption and separation performances.

A new class of conjugated polymers is prepared by means of a versatile palladium-catalyzed cyclopentannulation reaction using a series of specially designed diethynyl aryl synthons with the commercially available 9,10-dibromoanthracene DBA monomer.

The development of a simple and efficient synthetic methodology to engineer functional polymer materials for gas adsorption is necessary due to its relevance for various applications. Herein, we report the synthesis of metalorganic poly(vinylene sulfide) copolymers CTP1-3 with iron(II) clathrochelate of various side groups connected by tetraphenylbenzene units. CTP1-3 were subsequently oxidized into their respective poly(vinylene sulfone) copolymers CTP4-6 under green reaction conditions. The target copolymers CTP1-6 were characterized using various instrumental analysis techniques. Examination of the iodine adsorption properties of the copolymers revealed high iodine uptake properties, reaching 2360 mg g−1 for CTP2, and whose reusability tests proved its efficient regeneration, thus proving the importance of iron(II) clathrochelate polymers in iodine capture.

A design strategy is disclosed to synthesize conjugated microporous polymers (CMPs) using a versatile copper-catalyzed [4+2] cyclobenzannulation reaction, which employs a diphenylethynyl terephthalaldehyde derivative 3 with a series of triptycene-based...