Iridium(III) complex [Ir(ppy) 2 (tmBBI-H 2 )](PF 6 ) (IrBBI-H 2 ) has been exploited as an anion receptor. In this complex, the cis-diamine function of the bibenzimidazole is coupled in such a way to the photophysics of the iridium metal core that the photophysics is influenced by hydrogen bonds in the ligand periphery. Systematic studies on the complex reveal that IrBBI-H 2 is a convenient sensor for various anions under aerobic conditions and interacts with Cl -, Br -, I -, and HSO 4 by forming hydrogen bonds. Whereas H 2 PO 4 is only capable of mono-deprotonating IrBBI-H 2 , a stepwise process is operative when F - [a]
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