Cooperative Binding in a Fluorinated Nanoporous Polyketaminal Network for Highly Selective SF₆ and CF₄ Capture

Molecular recognition of chemically inert gases like SF 6 is often challenged by their inherently weak and nonspecific interactions with traditional adsorbents. Here, we synthesized a fluorinated nanoporous polyketaminal network, PKAN-1, engineered with a triad of synergistic binding sites (triazine, ketaminal, and fluorine). This architectural synergy creates an exceptionally specific trap, achieving a record SF 6 /N 2 selectivity (113) and high SF 6 uptake (2.40 mmol·g –1 ). A high isosteric heat of adsorption (−29.3 kJ·mol –1 ), corroborated by molecular simulations, provides definitive evidence for this cooperative binding mechanism. This work validates cooperative recognition as a powerful principle for designing adsorbents for challenging molecular targets.