Selective anion exchange and anion-tuned gas sorption in a phosphine coordination material




Riparetti, Ryan Douglas

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Herein we report a new ligand tris(4-(pyrid-4-yl)phenyl)phosphine sulfide (tppps) as a building block for the synthesis of a zeolite-like Phosphine Coordination Material (PCM). PCM-63 was made solvothermally with tppps and AgNO₃, producing off-white prisms. The material underwent selective anion exchange with PF₆ ̄ and ClO₄ ̄ over five other anions in a competition experiment. PCM-63 could remove 36.4% and 27.0% of 1 mM ReO₄ ̄ and ClO₄ ̄ in the presence of 100 mM Cl ̄, respectively. Four single-crystal to single-crystal studies were carried out with ReO₄ ̄, PF₆ ̄, ClO₄ ̄, and BF₄ ̄, each showing numerous CH···X (X = O, F) interactions between the framework and the anion. The anion-exchanged materials exhibited a large increase in surface areas for gases. Most notably, PCM-63-BF₄ and PCM-63-PF₆ exhibited a CO₂ surface area of 463 m²g⁻¹ and 466 m²g⁻¹, respectively. This is a large increase in surface area from PCM-63, which has a CO₂ surface area of 80 m²g⁻¹, suggesting that CH···F interactions stabilize the framework



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