The anticancer activities of dinuclear iridium(III) complexes [{Ir(tpy)Cl} 2 {μ-bb n }] 4+ {Cl-Irbb n ; tpy = 2,2Ј:6Ј,2ЈЈ-terpyridine, bb n = bis[4(4Ј-methyl-2,2Ј-bipyridyl)]-1,n-alkane (n = 7, 12 and 16)} against MCF-7 and MDA-MB-231 breast cancer cell lines have been determined. The activities of the Cl-Irbb n complexes increased with increasing chain length, the ClIrbb 16 complex showing the best anticancer properties. However, while Cl-Irbb 16 was active against the metastatic MDA-MB-231 cells (3 μM), it was relatively inactive against the nonmetastatic MCF-7 line (29 μM). The three geometric isomers of Cl-Irbb 16 were isolated and characterised by NMR spectroscopy and mass spectrometry, and their anticancer activities, lipophilicities (log P) and DNA-binding abilities were