Biphenyl Au(III) Complexes with Phosphine Ancillary Ligands: Synthesis, Optical Properties, and Electroluminescence in Light-Emitting Electrochemical Cells.

A series of ten cationic complexes of the general formula [(C^C)Au(P^P)]X, where C^C = 4,4'-di-tert-butyl-1,1'-biphenyl, P^P is a diphosphine ligand, and X is a noncoordinating counteranion, have been synthesized and fully characterized by means of chemical and X-ray structural methods. All the complexes display a remarkable switch-on of the emission properties when going from a fluid solution to a solid state. In the latter, long-lived emission with lifetime τ = 1.8-83.0 µs and maximum in the green-yellow region is achieved with moderate to high photoluminescence quantum yield (PLQY). This emission is ascribed to an excited state with a mainly triplet ligand-centered (3LC) nature. This effect strongly indicates that rigidification of the environment helps to suppress nonradiative decay, which is mainly attributed to the large molecular distortion in the excited state, as supported by density functional theory (DFT) and time-dependent DFT (TD-DFT) computation. In addition, quenching intermolecular interactions of the emitter are avoided thanks to the steric hindrance of the substituents. Emissive properties are therefore restored efficiently. The influence of both diphosphine and anion has been investigated and rationalized as well. Using two complexes as examples and owing to their enhanced optical properties in the solid state, the first proof-of-concept of the use of gold(III) complexes as electroactive materials for the fabrication of light-emitting electrochemical cell (LEC) devices is herein demonstrated. The LECs achieve peak external quantum efficiency, current efficiency, and power efficiency up to ca. 1%, 2.6 cd A-1, and 1.1 lm W-1 for complex 1PF6 and 0.9%, 2.5 cd A-1, and 0.7 lm W-1 for complex 3, showing the potential use of these novel emitters as electroactive compounds in LEC devices.

[(C C)Au(N N)]+ Complexes as a New Family of Anticancer Candidates: Synthesis, Characterization and Exploration of the Antiproliferative Properties.

A library of eleven cationic gold(III) complexes of the general formula [(C C)Au(N N)]+ when C C is either biphenyl or 4,4'-ditertbutyldiphenyl and N N is a bipyridine, phenanthroline or dipyridylamine derivative have been synthesized and characterized. Contrasting effects on the viability of the triple negative breast cancer cells MDA-MB-231 was observed from a preliminary screening. The antiproliferative activity of the seven most active complexes were further assayed on a larger panel of human cancer cells as well as on non-cancerous cells for comparison. Two complexes stood out for being either highly active or highly selective. Eventually, reactivity studies with biologically meaningful amino acids, glutathione, higher order DNA structures and thioredoxin reductase (TrxR) revealed a markedly different behavior from that of the well-known coordinatively isomeric [(C N C)Au(NHC)]+ structure. This makes the [(C C)Au(N N)]+ complexes a new class of organogold compounds with an original mode of action.