title: The effect of pyridinecarboxylate chelating groups on the stability and electronic relaxation of gadolinium complexes.
abstract: The ligand N,N'-bis[(6-carboxy-2-pyridylmethyl]ethylenediamine-N,N'-diacetic acid (H(4)bpeda) was synthesised using an improved procedure which requires a reduced number of steps and leads to a higher yield with respect to the published procedure. It was obtained in three steps from diethylpyridine-2,6-dicarboxylate and commercially available ethylenediamine-N,N[prime or minute]-diacetic acid with a total yield of approximately 20%. The crystal structure of the hexa-protonated form of the ligand which was determined by X-ray diffraction shows that the four carboxylates and the two amines are protonated. The crystal structure of the polynuclear complex [Gd(bpeda)(H(2)O)(2)](3)[Gd(H(2)O)(6)](2)Cl(3)(2), isolated by slow evaporation of a 1:1 mixture of GdCl(3) and H(4)bpeda at pH approximately 1, was determined by X-ray diffraction. In complex three [Gd(bpeda)(H(2)O)(2)] units, containing a Gd(III) ion ten-coordinated by the octadentate bpeda and two water molecules, are connected in a pentametallic structure by two hexa-aquo Gd(3+) cations through four carboxylato bridges. The protonation constants (pK(a1)= 2.9(1), pK(a2)= 3.5(1), pK(a3)= 5.2(2), and pK(a4)= 8.5(1)) and the stability constants of the complexes formed between Gd(III) and Ca(II) ions and H(4)bpeda (log beta(GdL)= 15.1(3); log beta(CaL)= 9.4(1)) were determined by potentiometric titration. The unexpected decrease in the stability of the gadolinium complex and of the calcium complex of the octadentate ligand bpeda(4-) with respect to the hexadentate ligand edta(4-) has been interpreted in terms of an overall lower contribution to stability of the metal-nitrogen interactions. The EPR spectra display very broad lines (apparent DeltaH(pp) approximately 800-1200 G at X-band and 90-110 G at Q-band depending on the temperature), indicating a rapid transverse electron spin relaxation. At X-band, Gd(bpeda) is among the fastest relaxing Gd(3+) complexes to date suggesting that the presence of pyridinecarboxylate chelating groups in itself does not lead to slow electron relaxation.
authors.affiliation: Laboratoire de Reconnaissance Ionique, Service de Chimie Inorganique et Biologique, Departement de Recherche Fondamentale sur la Matiere Condensee, CEA-Grenoble, 38054 Grenoble Cedex 09, France.
authors.forename: Nicholas
authors.initials: N
authors.lastname: Chatterton
authors.forename: Christelle
authors.initials: C
authors.lastname: Gateau
authors.forename: Marinella
authors.initials: M
authors.lastname: Mazzanti
authors.forename: Jacques
authors.initials: J
authors.lastname: Pécaut
authors.forename: Alain
authors.initials: A
authors.lastname: Borel
authors.forename: Lothar
authors.initials: L
authors.lastname: Helm
authors.forename: André
authors.initials: A
authors.lastname: Merbach
mesh_terms: D002264:Carboxylic Acids / Q000737:chemistry*; D002614:Chelating Agents / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy; D004583:Electrons; D005063:Europium / Q000737:chemistry; D005682:Gadolinium / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*; D012680:Sensitivity and Specificity
chemical_list: D002264:Carboxylic Acids; D002614:Chelating Agents; D008024:Ligands; D009942:Organometallic Compounds; D011725:Pyridines; D005063:Europium; D005682:Gadolinium