Water-Soluble Luminescent Cyclometalated Gold(III) Complexes with cis-Chelating Bis(N-Heterocyclic Carbene) Ligands: Synthesis and Photophysical Properties

Abstract

A new class of cyclometalated AuIII complexes containing various bidentate C-deprotonated C^N and cis-chelating bis(N-heterocyclic carbene) (bis-NHC) ligands has been synthesized and characterized. These are the first examples of AuIII complexes supported by cis-chelating bis-NHC ligands. [Au(C^N)(bis-NHC)] complexes display emission in solutions under degassed condition at room temperature with emission maxima (λmax) at 498–633 nm and emission quantum yields of up to 10.1 %. The emissions are assigned to triplet intraligand (IL) π->π* transitions of C^N ligands. The AuIII complex containing a C^N (C-deprotonated naphthalene-substituted quinoline) ligand with extended π-conjugation exhibits prompt fluorescence and phosphorescence of comparable intensity with λmax at 454 and 611 nm respectively. With sulfonate-functionalized bis-NHC ligand, four water-soluble luminescent AuIII complexes, including those displaying both fluorescence and phosphorescence, were prepared. They show similar photophysical properties in water when compared with their counterparts in acetonitrile. The long phosphorescence lifetime of the water-soluble AuIII complex with C-deprotonated naphthalene-substituted quinoline ligand renders it to function as ratiometric sensor for oxygen. Inhibitory activity of one of these water-soluble AuIII complexes towards deubiquitinase (DUB) UCHL3 has been investigated; this complex also displayed a significant inhibitory activity with IC50 value of 0.15 μM.