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 [M(2)L(2)](4+). In solution the free ligand was fluorescent with emission attributed to the coumarin fluorophores (lambda(em) = 437 nm). The luminescent properties of the corresponding dimetallic helicates complexes were examined and revealed that the Zn(2+) complex demonstrates enhanced emission when compared to the parent ligand, whereas Co(2+), Cu(2+), Cd(2+) and Hg(2+) induce varying degrees of fluorescence quenching. In particular, comparative luminescence measurements at 77 K and room temperature showed that the quenching mechanism for [Cu(2)L(2)](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.
A diamino-functionalised cryptate can react irreversibly with butanal in water, in the presence of an excess of a metal ion, to form a cyclised bis-aminal complex, which displays metal-dependent luminescence properties.
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