title: Solid state and solution dynamics of pyridine based tetraaza-macrocyclic lanthanide chelates possessing phosphonate ligating functionality (Ln-PCTMB): effect on relaxometry and optical properties.
abstract: The macrocyclic ligand 3,6,9-tris(methylenebutyl phosphonic acid)-3,6,9-15-tetraazabicyclo [9.3.1]pentadeca-1(15),11,13-triene (PCTMB) was synthesized and complexes of Eu(3+), Tb(3+), and Gd(3+) studied by X-ray crystallography, luminescence, and relaxometry. In the crystal these complexes are dimeric and possess 8-coordinate Ln(3+) centers that are linked by bridging phosphonates. The rigidity introduced by the pyridyl nucleus forces the EuPCTMB and TbPCTMB to adopt a twisted snub disphenoid (TSD) coordination geometry. Examination of the (5)D(0) --> (7)F(0) luminescent transition of EuPCTMB in the solid state confirmed the existence of a single distinct Eu(3+) coordination environment, whereas two Eu(3+) coordination environments were observed in aqueous solution. Lifetime analysis of aqueous TbPCTMB solutions determined that q = 0.1 and q = 1.0 for the two coordination environments and Stern-Volmer quenching constants (K(SV)(tau) = 1101 M(-1), K(SV)(Phi) = 40780 M(-1)) support the presence of a complicated monomer/dimer equilibrium. Relaxivity studies of GdPCTMB in H(2)O/CH(3)OH exhibited a concentration dependency (0.02 mM-10.00 mM) ranging from r(1) = 7.0 mM(-1) s(-1) to 4.0 mM(-1) s(-1) consistent with the trend observed by luminescence.
authors.affiliation: Macrocyclics, 2110 Research Row, Dallas, Texas 75235, USA. garry@macrocyclics.com
authors.forename: Garry E
authors.initials: GE
authors.lastname: Kiefer
authors.forename: Mark
authors.initials: M
authors.lastname: Woods
mesh_terms: D001372:Aza Compounds / Q000737:chemistry*; D002614:Chelating Agents / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D008024:Ligands; D047028:Macrocyclic Compounds / Q000138:chemical synthesis / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D055095:Optics and Photonics; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D063065:Organophosphonates / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*; D012996:Solutions
chemical_list: D001372:Aza Compounds; D002614:Chelating Agents; D028581:Lanthanoid Series Elements; D008024:Ligands; D047028:Macrocyclic Compounds; D009942:Organometallic Compounds; D063065:Organophosphonates; D011725:Pyridines; D012996:Solutions