Porous Cu(I) Triazolate Framework and Derived Hybrid Membrane with Exceptionally High Sensing Efficiency for Gaseous Oxygen

Phosphorescent complexes of precious metal ions are widely studied as optical sensing materials for molecular oxygen. Combining the advantages of luminescent complexes and porous matrixes, porous coordination polymers show great potential for oxygen‐sensing, although their sensitivity, requirement of precious metal, and device fabrication remain challenging issues. In this work, the photoluminescence and oxygen‐sensing properties of the porous Cu(I) triazolate framework [Cu(detz)] (MAF‐2, Hdetz = 3,5‐diethyl‐1,2,4‐trizole) is studied in detail, which shows high chemical stability in moisture and water, very long phosphorescent lifetime (116 μs) and large Stokes shift (14 562 cm −1 ), as well as considerable oxygen permeability (1.7 × 10 −11 mol cm −1 s −1 bar −1 ) at ambient conditions, giving rise to exceptionally high luminescence quenching efficiency of 99.7% at 1 bar O 2 ( I 0 / I 100 = 356) with a perfectly linear Stern‐Volmer plot ( K SV = 356 bar −1 , R 2 = 0.9998), fast response and good reversibility. Further, a counter‐diffusion crystal‐growth method was developed to fabricate MAF‐2 thin films protected by silicone rubbers as the first example of soft membrane oxygen sensor based on coordination polymer or metal‐organic framework, which exhibited extraordinary oxygen‐sensing performance (limit of detection = 0.047 mbar) and outstanding mechanical property, as well as outstanding chemical stability even in an acidic atmosphere.