Iridium(III) is often considered to be one of the most inert octahedral metal ions. Herein we present a phenanthroimidazole-based bis-cyclometalated iridium(III) chloride undergoing a facile chloro ligand exchange with iodine, in a gas-solid reaction under ambient conditions. Monitoring the progress of the reaction by X-ray diffraction analysis reveals the crystal-packing-induced exceptional stereoselectivity of this topochemical transformation. The results provide excellent opportunities to modulate the geometry and kinetic properties of cyclometalated iridium(III) complexes that may be very promising in catalysis and design of anticancer agents.

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A non-symmetric aromatic β-diketone enol bearing a carb­oxy­methyl group has been synthesized and characterized by X-ray crystallography, 1H and 13C NMR spectroscopy, elemental analysis, UV–Vis spectroscopy and cyclic voltammetry.