Tuning The Intracellular Distribution of [3+2+1] Iridium(III) Complexes In Bacterial And Mammalian Cells By iClick Reaction With Biomolecular Carriers Functionalized With Alkynone Groups.

Three iridium(III) triazolato complexes of the general formula [Ir(triazolato R,R' )(ppy)(terpy)]PF 6 with ppy=2-phenylpyridine and terpy=2,2':6',2''-terpyridine were efficiently prepared by iClick reaction of [Ir(N 3 )(ppy)(terpy)]PF 6 , with alkynes and alkynones, which allowed facile introduction of biological carriers such as biotin and cholic acid. In contrast to the precursor azido complex, which decomposed upon photoexcitation on a very short time scale, the triazolato complexes were stable in solution for up to 48 h. They emit in the spectral region around 540 nm with a quantum yield of 15-35 % in aerated acetonitrile solution and exhibit low cytotoxicity with IC 50 values >50 μM for most complexes in L929 and HeLa cells, demonstrating their high suitability as luminescent probes. Cell uptake studies with confocal luminescence microscopy in prokaryotic Gram-positive S. aureus and Gram-negative E. coli bacteria as well as eukaryotic mammalian L929 and HeLa cells showed significant uptake in particular of the cholic acid conjugates iridium(III) moiety and distinct intracellular distribution modulated by the nature of the peripheral functional groups that can easily be modified by the iClick reaction.