The potentially hexadentate ligand L, which contains two terminal coumarin fluorophores, forms dinuclear double-stranded helicates with dicationic metal ions, giving species of the generic form [M2L2]4+. In solution the free ligand was fluorescent with emission attributed to the coumarin fluorophores (λem = 437 nm). The luminescent properties of the corresponding dimetallic helicates complexes were examined and revealed that the Zn2+ complex demonstrates enhanced emission when compared to the parent ligand, whereas Co2+, Cu2+, Cd2+ and Hg2+ induce varying degrees of fluorescence quenching. In particular, comparative luminescence measurements at 77 K and room temperature showed that the quenching mechanism for [Cu2L2]4+ can be attributed to a photoinduced electron transfer. ESI-MS selectivity studies showed that in the presence of a mixture of metal dications no preference for any one metal ion was observed.