Search for: All records

Abstract Cyclotetrabenzil, a shape‐persistent macrocyclic octaketone, is found to undergo eightfold condensation with hydroxylamine hydrochloride to yield its octaoxime. Subsequent acetylation of this macrocyclic oxime afforded the corresponding octaoxime acetate. Single‐crystal X‐ray diffraction reveals that both new derivatives assemble into nanotubular structures. However, their packing differs: the oxime forms hydrogen‐bonded tubes that bundle via included dimethyl sulfoxide (DMSO) molecules, whereas the acetate—lacking hydrogen‐bond donors—forms more loosely packed tubes with molecules tilted ∼54.5° relative to the tube axis. Gas sorption studies (CO₂, C₂, and C₃hydrocarbons) show that cyclotetrabenzil is nonporous, whereas the oxime and acetate exhibit modest microporosity with BET surface areas of ∼200 m²g⁻¹. Both derivatives display preferential uptake of propyne over propene and propane, and the acetate also adsorbs more acetylene than ethylene or ethane. Nonetheless, these capacities and selectivities are suboptimal for dynamic separation of C₂and C₃hydrocarbons. This study illustrates how oxime functionalization can modulate macrocyclic assembly and gas uptake behavior, providing insights for the design of future porous organic macrocycles. 

Abstract The recovery and separation of organic solvents is highly important for the chemical industry and environmental protection. In this context, porous organic polymers (POPs) have significant potential owing to the possibility of integrating shape‐persistent macrocyclic units with high guest selectivity. Here, we report the synthesis of a macrocyclic porous organic polymer (np‐POP) and the corresponding model compound by reacting the cyclotetrabenzil naphthalene octaketone macrocycle with 1,2,4,5‐tetraaminobenzene and 1,2‐diaminobenzene, respectively, under solvothermal conditions. Co‐crystallization of the macrocycle and the model compound with various solvent molecules revealed their size‐selective inclusion within the macrocycle. Building on this finding, thenp‐POP with a hierarchical pore structure and a surface area of 579 m² g⁻¹showed solvent uptake strongly correlated with their kinetic diameters. Solvents with kinetic diameters below 0.6 nm – such as acetonitrile and dichloromethane – showed high uptake capacities exceeding 7 mmol g⁻¹. Xylene separation tests revealed a high overall uptake (~34 wt %), witho‐xylene displaying a significantly lower uptake (~10 wt % less than other isomers), demonstrating the possibility of size and shape selective separation of organic solvents. 

Abstract The development of porous materials is of great interest for the capture of CO₂from various emission sources, which is essential to mitigate its detrimental environmental impact. In this direction, porous organic polymers (POPs) have emerged as prime candidates owing to their structural tunability, physiochemical stability and high surface areas. In an effort to transfer an intrinsic property of a cyclotetrabenzoin‐derived macrocycle – its high CO₂affinity – into porous networks, herein we report the synthesis of three‐dimensional (3D) macrocycle‐based POPs through the polycondensation of an octaketone macrocycle with phenazine‐2,3,7,8‐tetraamine hydrochloride. This polycondensation was performed under ionothermal conditions, using a eutectic salt mixture in the temperature range of 200 to 300 °C. The resulting polymers, named 3D‐mmPOPs, showed reaction temperature‐dependent surface areas and gas uptake properties. 3D‐mmPOP‐250 synthesized at 250 °C exhibited a surface area of 752 m² g⁻¹and high microporosity originating from the macrocyclic units, thus resulting in an excellent CO₂binding enthalpy of 40.6 kJ mol⁻¹and CO₂uptake capacity of 3.51 mmol g⁻¹at 273 K, 1.1 bar.