On bio-MOF materials doped with phosphorescent iridium complexes for molecular oxygen determination: Synthesis,...

In this paper, two phosphorescent Ir(III) complexes, Ir(ppy)₂(Ln), were synthesized using 2-phenyl pyridine (ppy) as the first (major) ligand and two phosphorous compounds (L1 and L2) as the auxiliary ligand. Their single crystal structure and electronic structure were discussed. Ir(ppy)₂(Ln) complexes were doped into a supporting matrix of bio-MOF-1 via cationic exchange to ensure their uniform distribution. Their successful doping was confirmed by SEM, fluorescence microscopy image, XRD, N₂ adsorption/desorption and ICP measurement. Their photophysical parameters, including absorption spectra, excitation spectra, emission spectra, emission lifetime and quantum yield, were discussed in detail. Their phosphorescent emission was confirmed by density functional theory and emission lifetime, making them applicable for oxygen sensing. Linear working curves were observed for both composite samples, showing sensitivity as high as 23.65 with response/recovery time of 9/22 s. Humidity effect on sensing performance was limited. These parameters were found superior to literature ones based on phosphorescent Cu(I), RE(III), Ru(II) and Re(I) complexes. The sensing mechanism was revealed as a dynamic collision between Ir(ppy)₂(Ln) and O₂ molecules. The novelty of this work was the combination of phosphorescent Ir(III) complexes with porous bio-MOF-1, resulting in greatly improved sensitivity and linear sensing with short response time.