Amino group-driven distinguishing homocysteine from cysteine and glutathione in photoluminesecent signal of the iridium(III) complexes

Abstract

In this work, six iridium(III) complexes have been designed, synthesized and characterized. The molecular structures of complex 1 ([(pba)₂Ir(bpy-2N(CH₃)₂)]PF₆), 2 ([(pba)₂Ir(bpy-2NH₂)]PF₆) and 3 ([(pba)₂Ir(bpy-2CH₃)]PF₆) were determined by single crystal X-ray diffraction. Upon addition of Hcy (homocysteine) to the solution of complex 1, a luminescent variation from orange red to green was observed by the naked eye, corresponding to a large blue shift from 604 nm to 498 nm (~106 nm). While the emission intensity of complex 1 was almost no change after addition of other common amino acids including Cys (cysteine) and GSH (glutathione). The aldehyde group of complex 1 formed a new thiazinane/thiazolidine ring with Hcy/Cys confirmed by ¹H NMR and high-resolution mass spectrometry. And the new product 1-Hcy had a higher quantum yield than 1-Cys. Theoretical calculations showed that the HOMO (highest occupied molecular orbital) of 1-Hcy was located on the newly formed six-membered thiazinane ring, which was different from the HOMO of 1-Cys. Compared with the other iridium(III) complexes, we can speculate that the large blue shift and enhancement of the emission intensity of the complex 1 were related to the strong electron donating ability of the modified amino groups on bipyridine ligand. This will provide an idea for the design of ratio-based luminescence probes for Hcy in future.