Octavia A. Blackburn

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The first lanthanide cation-templated synthesis of an interlocked structure is demonstrated through an interpenetrated assembly between a pyridine N-oxide threading component coordinating to a lanthanide cation complexed within a macrocycle. Stoppering of the pseudo-rotaxane assembly allows for preparation of the [2]rotaxane.
Fluoride binding by a series of europium and ytterbium complexes of DOTA-tetraamide ligands derived from primary, secondary and tertiary amides has been studied by NMR and luminescence spectroscopies. In all the systems studied, fluoride binding results in a change in the nature of the magnetic anisotropy at the metal centre from an easy axis, to an easy(More)
Addition of fluoride to aqueous solutions of lanthanide complexes of DTMA results in the formation of ternary complexes of the form [F·Ln·DTMA](2+) in which an axial solvent molecule is displaced by fluoride. [F·Ln·DTMA](2+) and [H2O·Ln·DTMA](3+) are in exchange on a timescale of around 1 s. Dramatic changes are observed in both the NMR and luminescence(More)
Binuclear lanthanide complexes consisting of two lanthanide binding domains in kinetically stable DO3A binding pockets linked by a 3-functionalized meta-xylyl bridge form stable 1:1 adducts with isophthalate and dinicotinate in water. The influence of buffer, pH and ligand structure on the binding of dinicotinate has been investigated.
Cyanide ions are shown to interact with lanthanide complexes of phenacylDO3A derivatives in aqueous solution, giving rise to changes in the luminescence and NMR spectra. These changes are the consequence of cyanohydrin formation, which is favored by the coordination of the phenacyl carbonyl group to the lanthanide center. These complexes display minimal(More)
Lanthanide complexes of tetrapicolyl cyclen displayed remarkably high affinities for fluoride (log K≈5) in water, and were shown to form 1:1 complexes. The behaviour of these systems can be rationalised by changes to the magnitude of the crystal-field parameter, B20 . However, such changes are not invariably accompanied by a change in sign of this(More)
Yb⋅DTMA forms a ternary complex with fluoride in aqueous solution by displacement of a bound solvent molecule from the lanthanide ion. [Yb⋅DTMA⋅F]2+ and [Yb⋅DTMA⋅OH2]3+ are in slow exchange on the relevant NMR timescale (<2000 s-1), and profound differences are observed in their respective NMR and EPR spectra of these species. The observed differences can(More)
A large series of complexes has been synthesized with two chelating, Schiff base azobenzene derivatives connected linearly by coordination to a central nickel(II) or palladium(II) ion. These compounds have the general formulas M(II)(OC(6)H(3)-2-CHNR-4-N═NC(6)H(4)-4-CO(2)Et)(2) [M = Ni; R = n-Bu (3c), n-C(6)H(13) (3d), n-C(8)H(17) (3e), n-C(12)H(25) (3f), Ph(More)
A heterotrimetallic tetranuclear lanthanide complex containing two dysprosium ions, a terbium ion and a europium ion has been prepared by coupling three kinetically stable complexes together using the Ugi reaction. The covalently linked trimetallic system exhibits luminescence from all the different lanthanide centres.
A study of the anion-binding properties of three structurally related lanthanide complexes, which all contain chemically identical anion-binding motifs, has revealed dramatic differences in their anion affinity. These arise as a consequence of changes in the substitution pattern on the periphery of the molecule, at a substantial distance from the binding(More)