Cationic Iridium(III) Complex Containing both Triarylboron and Carbazole Moieties as a Ratiometric Fluoride Probe That Utilizes a Switchable Triplet–Singlet Emission

Abstract

A novel cationic Ir(III) complex [Ir(Bpq)(2)(CzbpyCz)]PF(6) (Bpq=2-[4-(dimesitylboryl)phenyl]quinoline, CzbpyCz = 5,5'-bis(9-hexyl-9H-carbazol-3-yl)-2,2'-bipyridine) containing both triarylboron and carbazole moieties was synthesized. The excited-state properties of [Ir(Bpq)(2)(CzbpyCz)]PF(6) were investigated through UV/Vis absorption and photoluminescence spectroscopy and molecular-orbital calculations. This complex displayed highly efficient orange-red phosphorescent emission with an emission peak of 583 nm and quantum efficiency of Phi=0.30 in dichloromethane at room temperature. The binding of fluoride ions to [Ir(Bpq)(2)(CzbpyCz)]PF(6) can quench the phosphorescent emission from the Ir(III) complex and enhance the fluorescent emission from the N--N ligand, which corresponds to a visual change in the emission from orange-red to blue. Thus, both colorimetric and ratiometric fluoride sensing can be realized. Interestingly, an unusual intense absorption band in the visible region was observed. And the detection of F(-) ions can also be carried out with visible light as the excitation wavelength. More importantly, the linear response of the probe absorbance change at lambda=351 nm versus the concentration of F(-) ions allows efficient and accurate quantification of F(-) ions in the range 0-50 microM.