Year: 2024
Type: article
Abstract: The development of more energy‐efficient separation technologies is essential. Especially the separation of cyclic aliphatic hydrocarbons from their aromatic counterparts remains a significant challenge due to azeotrope formation and similar physical properties, often requiring energy‐intensive processes. Herein, we introduce a novel class of electron‐deficient macrocycles with a unique rectangular structure to optimise interactions within the pore, enabling the highly selective molecular sieving of aromatic compounds from mixtures. Utilising dynamic covalent imine chemistry, the squareimine NDI 2 F4 2 ‐based crystalline functional material is directly obtained from the reaction mixture in a single self‐assembly step in high yields of 83 %, alongside the larger NDI 2 F8 2 congener, which can be obtained in 69 % yield. In vapour sorption and diffusion experiments, NDI 2 F4 2 demonstrates rapid adsorption kinetics with selectivities of 97 : 3 for benzene over cyclohexane and 93 : 7 for toluene over methylcyclohexane, while single‐crystal and powder X‐ray diffraction studies indicate that the selectivity is primarily governed by directed interactions between the electron‐deficient panels and aromatic guests.
Institution: Heinrich Heine University Düsseldorf
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $5,510
OpenAlex ID: W4404192619