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

Molecular recognition of chemically inert gases like SF₆ 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 SF₆/N₂ selectivity (113) and high SF₆ 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.