Ammonia Storage in Hydrogen Bond-Rich Microporous Polymers

The fascinating structural flexibility of porous polymers is highly attractive because it can result in optimized materials with specific host–guest interactions. Nevertheless, the fundamental mechanisms responsible for controlling the weak interactions of these hydrogen bond-rich networks—essential for developing smart task-specific materials used in recognition, capture, and sequestration processes—remain unexplored. Herein, by systematically comparing performance changes between poly(amic acid) (PAA)- and polycyclic imide (PI)-based porous polymers before and after NH3adsorption, the role of hydrogen bonds in conformational lability and responsiveness toward guest molecules is highlighted. By combining thermal gravimetric analysis with neutron spectroscopy supported by DFT calculations, we demonstrate that PAA’s chemical and physical stability is enhanced by the presence of stronger host–guest interactions. This observation also emphasizes the idea that efficient adsorption relies on having a high number of sites, upon which gas molecules can adsorb with greater affinity via strong hydrogen bonding interactions.