title: An iridium(III) complex of oximated 2,2'-bipyridine as a sensitive phosphorescent sensor for hypochlorite.
abstract: The designed synthesis of a sensitive phosphorescent chemosensor [Ir(ppy)(2)(L1)](PF(6)) (1) (Hppy = 2-phenylpyridine, L1 = 4'-methyl-2,2'-bipyridyl-4-carbaldehyde oxime) was carried out for selective detection of hypochlorite (ClO(-)). Complex 1 is weakly emissive in solution at ambient temperature due likely to rapid isomerization of C=N-OH as an effective non-radiative decay process. When 1 reacts with ClO(-), however, the emission is remarkably enhanced, in which the oxime in L1 is converted to a carboxylic acid in L2 (4'-methyl-2,2'-bipyridine-4-carboxylic acid). The produced complex [Ir(ppy)(2)(L2)](PF(6)) (2) exhibits bright orange-yellow luminescence originating from [5d(Ir) → π*(bpy)] (3)MLCT and [π(ppy) → π*(bpy)] (3)LLCT triplet excited states as suggested from the DFT computational studies. The selective and competitive experiments reveal that complex 1 shows high sensing selectivity and sensitivity for ClO(-) over other reactive oxygen species (ROS) and metal ions.
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China.
authors.forename: Na
authors.initials: N
authors.lastname: Zhao
authors.forename: Yu-Hui
authors.initials: YH
authors.lastname: Wu
authors.forename: Rui-Min
authors.initials: RM
authors.lastname: Wang
authors.forename: Lin-Xi
authors.initials: LX
authors.lastname: Shi
authors.forename: Zhong-Ning
authors.initials: ZN
authors.lastname: Chen
mesh_terms: D015082:2,2'-Dipyridyl / Q000737:chemistry; D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D006997:Hypochlorous Acid / Q000032:analysis*; D007495:Iridium / Q000737:chemistry; D007536:Isomerism; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010091:Oximes / Q000737:chemistry; D011789:Quantum Theory; D013056:Spectrophotometry, Ultraviolet
chemical_list: D056831:Coordination Complexes; D009942:Organometallic Compounds; D010091:Oximes; D007495:Iridium; D015082:2,2'-Dipyridyl; D006997:Hypochlorous Acid