title: Remarkable tuning of the photophysical properties of bifunctional lanthanide tris(dipicolinates) and its consequence on the design of bioprobes.
abstract: Derivatives of dipicolinic acid with a polyoxyethylene pendant arm at the pyridine 4-position have been functionalized for potential grafting with biological material. Four ligands with different terminal functions (alcohol, methoxy, phtalimide and amine) have been synthesized, which react with trivalent lanthanide ions Ln (III) to yield triple helical [Ln(L) 3] (3-) complexes, as shown by NMR and UV-vis titrations. The tris chelates display large thermodynamic stability with log beta 13 approximately 19-20 for all Eu (III) complexes for instance. Photophysical measurements reveal adequate sensitization of the metal-centered luminescence in the europium (eta sens = 33-72%) and terbium complexes, which is modulated by the nature of the terminal function. The lifetimes of the metal-centered excited states are long, up to 1.4 ms for [Eu(L) 3] (3-) and 1.6 ms for [Tb(L) 3] (3-) at room temperature, in line with hydration numbers essentially equal to zero. Quantum yields are as high as 29% for the [Eu( L ( NH2 )) 3] (3-) and 18% for the [Tb( L ( OH )) 3] (3-) tris chelates in water at physiological pH. These series of complexes demonstrate the extent of fine-tuning achievable for lanthanide luminescent probes and are simple models for investigating the effect of binding to biological molecules on the metal-centered luminescent properties.
authors.affiliation: Ecole Polytechnique Fédérale de Lausanne, Laboratory of Lanthanide Supramolecular Chemistry, Lausanne, Switzerland.
authors.forename: Anne-Laure
authors.initials: AL
authors.lastname: Gassner
authors.forename: Céline
authors.initials: C
authors.lastname: Duhot
authors.forename: Jean-Claude
authors.initials: JC
authors.lastname: G Bünzli
authors.forename: Anne-Sophie
authors.initials: AS
authors.lastname: Chauvin
mesh_terms: D003432:Cross-Linking Reagents / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D008024:Ligands; D049449:Luminescence; D049408:Luminescent Agents / Q000737:chemistry*; D010848:Picolinic Acids / Q000737:chemistry*
chemical_list: D003432:Cross-Linking Reagents; D028581:Lanthanoid Series Elements; D008024:Ligands; D049408:Luminescent Agents; D010848:Picolinic Acids; C004860:dipicolinic acid