Enhancing P NMR relaxation rates with a kinetically inert gadolinium complex.

The kinetically stable heptadentate gadolinium complex Gd.pDO3A (1.Gd) demonstrates significant 31P nuclear magnetic resonance (NMR) relaxation enhancement of biologically relevant phosphate species; adenosine triphosphate (ATP), phosphocreatine (PCr) and inorganic phosphate.

Lanthanide Complexes that Respond to Changes in Cyanide Concentration in Water.

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 affinity for fluoride and can detect cyanide at concentrations less than 1 μm.

Kinetically Inert Lanthanide Complexes as Reporter Groups for Binding of Potassium by 18-crown-6.

The barcode-like spectrum of lanthanide-centered emission has been used in imaging and to make responsive luminescent reporters. The intensities and the shapes of each line in the luminescence spectrum can also report on the coordination environment of the lanthanide ion. Here, we used lanthanide-centered emission to report on the binding of potassium in an 18-crown-6 binding pocket.

Luminescence of a binuclear europium complex bearing a 4-nitrophenolate chromophore: a different way of seeing pH dependence.

A europium complex derived from NP-(DO3A)2 exhibits pH-dependent europium-centred luminescence following excitation of the nitrophenolate chromophore. Such behaviour is not observed with an analogous mononuclear complex, suggesting coordination of both lanthanide ions to the phenolate oxygen in the emissive species.

Ratiometric oxygen sensing using lanthanide luminescent emitting interfaces.

Herein we describe the first example of a ratiometric lanthanide luminescent oxygen sensing interface. Immobilisation of terbium and europium cyclen complexes on glass substrates was achieved by a novel aryl nitrene photografting approach. The resulting interfaces demonstrated a ratiometric oxygen response between 0 and 0.

Controlling energy transfer in ytterbium complexes: oxygen dependent lanthanide luminescence and singlet oxygen formation.

Pyrene-appended ytterbium complexes have been prepared using Ugi reactions to vary the chromophore-lanthanide separation. Formation of the ytterbium(iii) excited state is sensitised via both the singlet and triplet excited states of the chromophore. Energy transfer from the latter is relatively slow, and gives rise to oxygen-dependent luminescence.

Reversible redox modulation of a lanthanide emissive molecular film.

Herein we demonstrate redox switchable emission from a sensitised, europium-ferrocene containing, molecular film assembled by a novel nitrene-based strategy. Electrochemical modulation of europium emission upon switching the ferrocene moiety's redox state is ascribed to the reversible generation of a quenching ferrocenium species.

Lanthanide complexes of azidophenacyl-DO3A as new synthons for click chemistry and the synthesis of heterometallic lanthanide arrays.

Lanthanide complexes of azidophenacyl DO3A are effective substrates for click reactions with ethyne derivatives, giving rise to aryl triazole appended lanthanide complexes, in which the aryl triazole acts as an effective sensitising chromophore for lanthanide luminescence. They also undergo click chemistry with propargylDO3A derivatives, giving rise to heterometallic complexes.

Kinetically Stable Lanthanide Complexes Displaying Exceptionally High Quantum Yields upon Long-Wavelength Excitation: Synthesis, Photophysical Properties, and Solution Speciation.

We demonstrate how highly emissive, kinetically stable complexes can be prepared using the macrocyclic scaffold of DO3A bearing coordinating aryl ketones as highly effective sensitizing chromophores. In the europium complexes, high quantum yields (up to 18% in water) can be combined with long-wavelength excitation (370 nm). The behavior in solution upon variation of pH, studied by means of UV-vis absorption, emission, and NMR spectroscopies, reveals that the nature of the chromophore can give rise to pH-dependent behavior as a consequence of deprotonation adjacent to the carbonyl group.

Ligation driven (19)F relaxation enhancement in self-assembled Ln(III) complexes.

Strong bidentate ligation between a fluorinated isophthalate and binuclear lanthanide-DO3A species yields a new class of (19)F NMR agent with very high nuclear relaxation rates at physiologically-relevant pH.

Spectrally resolved confocal microscopy using lanthanide centred near-IR emission.

The narrow, near infrared (NIR) emission from lanthanide ions has attracted great interest, particularly with regard to developing tools for bioimaging, where the long lifetimes of lanthanide excited states can be exploited to address problems arising from autofluorescence and sample transparency. Despite the promise of lanthanide-based probes for near-IR imaging, few reports on their use are present in the literature. Here, we demonstrate that images can be recorded by monitoring NIR emission from lanthanide complexes using detectors, optical elements and a microscope that were primarily designed for the visible part of the spectrum.

A lanthanide based sensor for the time-gated detection of hydrogen sulfide.

A kinetically stable Eu(III) complex for the detection of sulfide in water is reported. The probe shows excellent selectivity and fast reaction time. Its long-lived luminescence makes this the first probe for the time-gated detection of sulfide in complex biological samples.

Using remote substituents to control solution structure and anion binding in lanthanide complexes.

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 pocket. Herein, we explore these remote substituent effects and explain the observed behaviour through discussion of the way in which remote substituents can influence and control the global structure of a molecule through their demands upon conformational space.

Ternary self-assemblies in water: forming a pentanuclear ReLn4 assembly by association of binuclear lanthanide binding pockets with fac-Re(CO)3(dinicotinate)2Cl.

The self-assembly of higher order structures in water is realised by using the association of 1,3-biscarboxylates to binuclear meta-xylyl bridged DO3A complexes. Two dinicotinate binding sites are placed at a right-angle in a rhenium complex, which is shown to form a 1 : 2 complex with α,α'-bis(Eu·DO3A)-5-amino-m-xylene.

Reversible recruitment and emission of DO3A-derived lanthanide complexes at ligating molecular films on gold.

The recruitment of DO3A-derived lanthanide complexes by ligation to isophthalic acid and catechol-modified gold surfaces, and their resulting sensitization, is reported herein. Predictably pH-dependent surface recruitment is associated with the expected fingerprint europium and terbium emission characteristics. The intensity of the lanthanide luminescence scales exponentially with spacer length, indicating a strong quenching interaction between the lanthanide and the gold surface.

Ln2M complexes (M = Ru, Re) derived from a bismacrocyclic ligand containing a 4,4'-dimethyl-2,2'-bipyridyl bridging unit.

Homodinuclear lanthanide complexes derived from a ligand featuring two DO3A chelating sites linked by a 4,4'-dimethyl-2,2'-bipyridyl spacer were prepared and characterized. The bipyridyl coordination site of 1 was used to introduce Ru(Bpy)(2) and Re(CO)(3)Cl moieties, leading to the formation of heterometallic d-f(2) complexes with general formulae [Ln(2)·1·Ru(Bpy)(2)](2+) (Ln = Nd, Eu, Tb, Yb and Lu) and [Ln(2)·1·Re(CO)(3)Cl] (Ln = Nd, Yb and Lu). The luminescence properties of the complexes were investigated by means of absorption spectroscopy and steady-state and time-resolved luminescence spectroscopy covering the visible and NIR regions.

Preparation and study of an f,f,f',f'' covalently linked tetranuclear hetero-trimetallic complex - a europium, terbium, dysprosium triad.

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.

Luminescence and upconversion from thulium(III) species in solution.

Thulium salts and complexes are shown to be emissive from three states in the excited state manifold of Tm(3+). Formation of the (1)D(2) state can result in luminescence, or in energy transfer to the lower energy (1)G(4) and (3)H(4) emissive states. Where chromophores are present in the ligand structure, emission is restricted to thulium centred emissive states that are lower in energy than the chromophore centred donor state.

Lanthanide complexes of DOTA monoamide derivatives bearing an isophthalate pendent arm.

An isophthalate-bearing DOTA monoamide derivative has been synthesised and used to prepare a family of lanthanide complexes. Luminescence and NMR studies in solution show that the predominant form of the complexes in solution is a mono-capped square antiprism about the lanthanide centre, in which a solvent molecule occupies the ninth coordination site. The crystal structure of the terbium complex is presented and is in close agreement with the solution state data.

A family of 13 tetranuclear zinc(II)-lanthanide(III) complexes of a [3+3] Schiff-base macrocycle derived from 1,4-diformyl-2,3-dihydroxybenzene.

A family of thirteen tetranuclear heterometallic zinc(II)-lanthanide(III) complexes of the hexa-imine macrocycle (L(Pr))(6-), with general formula Zn(II)(3)Ln(III)(L(Pr))(NO(3))(3)·xsolvents (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm or Yb), were prepared in a one-pot synthesis using a 3:1:3:3 reaction of zinc(II) acetate, the appropriate lanthanide(III) nitrate, the dialdehyde 1,4-diformyl-2,3-dihydroxybenzene (H(2)L(1)) and 1,3-diaminopropane. A hexanuclear homometallic zinc(II) macrocyclic complex [Zn(6)(L(Pr))(OAc)(5)(OH)(H(2)O)]·3H(2)O was obtained using a 2:0:1:1 ratio of the same reagents. A control experiment using a 1:0:1:1 ratio failed to generate the lanthanide-free [Zn(3)(L(Pr))] macrocyclic complex.

Reversible luminescence switching of a redox-active ferrocene-europium dyad.

The copper-catalyzed cycloaddition reaction between a propargyl-appended europium complex and azidomethylferrocene yields a d-f dyad whose photophysical properties can be reversibly switched by varying the oxidation state of the ferrocene chromophore.

Thermodynamics of core metal replacement and self-assembly of Ca(2+) 15-metallacrown-5.

The equilibria for core Ca(2+) replacement by Ln(3+) in copper(II) 15-MC-5 complexes have been investigated using a series of visible spectrophotometric titrations of calcium(II) metallacrowns ({Ca(II)[15-MC(Cu(II)(N)(L))-5]}(2+)) with Ln(3+) ions (H(2)L = pheha, (S)-alpha-phenylalaninehydroxamic acid, or trpha, (S)-alpha-tryptophanhydroxamic acid). These studies allowed the determination of the equilibrium constants for the reaction {Ca(II)[15-MC(Cu(II)(N)(L))-5]}(2+) + Ln(3+) --> {Ln(III)[15-MC(Cu(II)(N)(L))-5]}(3+) + Ca(2+) in methanol/water 9:1 (Ln(3+) = La(3+), Gd(3+), Dy(3+), Er(3+)) or 99:1 (Ln(3+) = La(3+), Nd(3+), Gd(3+), Dy(3+), Er(3+), Yb(3+)), respectively. The log K for these reactions decreases with increasing atomic number of the lanthanide(III), ranging from 6.

Thermodynamics of binding of carboxylates to amphiphilic Eu(3+)/Cu(2+) metallacrown.

The binding constants of acetate and benzoate to a Pheha-based 15-metallacrown-5 have been determined by a fluorimetric indicator displacement assay demonstrating on a thermodynamic basis the stabilization effect arising from complexation of the less polar carboxylate into the hydrophobic pocket of the metallacrown scaffold.