Structural Diversity in Cyclometalated Diiridium(III) Complexes with Bridging syn and anti μ2‐Oxamidato and μ2‐Dithioxamidato Ligands

Six new diiridium complexes containing 2‐methyl‐6‐phenylpyridyl as the cyclometalating ligand with a μ2‐oxamidato or μ2‐dithioxamidato bridge have been synthesized in 60‐73% yields. These were revealed by multinuclear NMR spectroscopy to contain inseparable mixtures of diastereomers (rac, DD/LL and meso, DL) bridges anti syn configurations. The remarkable variety isomers present was confirmed X‐ray crystallography on single crystals grown from each complex. In one complex N,N′‐bis(4‐trifluoromethylphenyl)‐μ2‐oxamidato bridge, two structurally determined. Two found rac meso forms isomer. Hybrid DFT computations four negligible energetic preferences for isomer despite methyl groups ligands being close neighboring thus supporting experimental findings mixtures. distinct broad emissions maxima at 522‐529 nm 689‐701 observed these dichloromethane are attributed mixed metal‐ligand charge transfer (MLLCT) excited states involving pyridyl moieties respectively aid electronic structure computations.