Two new tetraazamacrocyclic ligands are designed with the aim of sensitizing the luminescence of Tb(III) and Eu(III) ions in water: L5 [1,4,7,10-tetrakis[N-(phenacyl)carbamoylmethyl]-1,4,7,10-tetraazacyclododecane] and L6 [1,4,7,10-tetrakis[N-(4-phenylphenacyl)carbamoylmethyl]-1,4,7,10-tetraazacyclododecane]. These ligands react with lanthanide trifluoromethanesulfonates to yield stable 1:1 complexes in water (log K = 12.89 +/- 0.15 for EuL5). X-ray diffraction on [Tb(L5)(H(2)O)](CF(3)SO(3))(3) (P1 macro, a = 13.308(3) A, b = 14.338(3) A, c = 16.130(3) A, alpha = 101.37(3) degrees, beta = 96.16(3) degrees, gamma = 98.60(3) degrees ) shows the Tb(III) ion lying on a C(4) axis and being 9-coordinate, with one water molecule bound in its inner coordination sphere. The absolute quantum yields are determined in aerated water for the complexes formed with ions used in fluoroimmunoassays (Ln = Sm, Eu, Tb, and Dy). Large values are found for [Tb(H(2)O)(L5)](3+) and [Eu(H(2)O)(L6)](3+), in line with the molecular design of the receptors: 23.1% and 24.7%, respectively. The intense luminescence of these ions results from efficient intersystem crossing and L --> Ln energy transfer processes, as well as from a suitable shielding of the emitting ions from radiationless deactivation.

A new macrocyclic ligand, L3, has been synthesised, based on the cyclen framework grafted with three phenacyl light-harvesting groups and a C5-alkyl chain bearing a carboxylic acid function as a potential linker for biological material. Acidity constants are determined by spectrophotometric titrations, as well as conditional stability constants for the resulting 1:1 complexes with trivalent lanthanide ions. The complexes have stabilities comparable to 1,4,7,10-tetrakis(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane (dtma) complexes, with pLn approximately 12-13. Photophysical properties of the ligand and of the EuL3 and TbL3 complexes have been determined for both microcrystalline samples and solutions in water and acetonitrile. They point to the metal ion being present in an environment with axial symmetry derived from the C4 point group. The hydration number determined for TbL3 decreases with increasing pH value and becomes fractional at pH 7.5, which points to an equilibrium between two differently solvated species and probably to the participation of the deprotonated carboxylic acid chain in the complexation. The quantum yields in water (1.9% for EuIII, 3.4% for TbIII) are smaller than those for complexes with the symmetrically substituted parent macrocycle, but efficient luminescence resonant energy transfer (LRET) was observed when Cy5 dye was added to the solutions. Finally, the influence of the TbL3 complex on cell viability is tested on both malignant (5D10 mouse hybridoma, Jurkat human T leukaemia, MCF-7 human breast carcinoma) and non-malignant (Hacat human keratinocyte) cell lines. Cell viability after 24 h incubation at 37 degrees C with 500 microM TbL3 was >90% for all cell lines, except Jurkat (>70%). All of these properties make LnL3 complexes interesting potential probes for bioanalyses.

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