Self-assembly between dicarboxylate ions and a binuclear europium complex: formation of stable adducts and heterometallic lanthanide complexes

Tilney, James A.; Sørensen, Thomas Just; Burton‐Pye, Benjamin P.; Faulkner, Stephen

doi:10.1039/c1dt11103e

Cited by 46 publications

(53 citation statements)

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“…Analysis using Dynafit[6, 11] gave an equilibrium constant of 9.4 m −1 with a 95 % confidence interval from 7.6 to 11.4 m −1 . This value is similar to that determined for a related Eu tetraamide complex, suggesting that it reflects the local donor environment and the residual charge on the lanthanide.…”

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confidence: 99%

Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb⋅DTMA]³⁺ in Aqueous Solution

et al. 2015

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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 be explained by drastic modification of the ligand field states due to the fluoride binding. This changes the magnetic anisotropy of the YbIII ground state from easy-axis to easy-plane type, and this change is easily detected in the observed magnetic anisotropy despite thermal population of more than just the ground state. The spectroscopic consequences of such drastic changes to the ligand field represent important new opportunities in developing fluoride-responsive complexes and contrast agents.

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Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb⋅DTMA]³⁺ in Aqueous Solution

et al. 2015

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“…Indeed, self-assembly of such heterometallic lanthanide complexes has only recently been observed, through exploiting the affinity of m-xylyl bridged DO3A derivatives for an isophthalate appended DOTA monoamide (Fig. 9.18) [66]. This system is remarkable in the high affinity of the host for the guest even in competitive media: the binding constant is unaltered in competitive media such as phosphate buffered saline, suggesting that self-assemblies could have potential in vivo.…”

Section: Heterometallic Complexes Derived From Bridging and Multi-commentioning

confidence: 99%

Heterometallic Complexes Containing Lanthanides

Faulkner

Tropiano

2014

Luminescence of Lanthanide Ions in Coordination Compounds and Nanomaterials

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The synthesis of tetranuclear gold complexes, as tructurally unprecedented octanuclear complex with ap lanar [Au I 8 ]c ore,a nd pentanuclear [Au I 4 M I ](M = Cu, Ag) complexes is presented. The linear [Au I 4 ]complex undergoes C À Hf unctionalization of carbonyl compounds under mild reaction conditions.I na ddition, [Au I 4 Ag I ]c atalyzes the carbonylation of primary amines to form ureas under homogeneous conditions with efficiencies higher than those achieved by gold nanoparticles. Following the pioneering work of the groups of Hutchings [1] and Haruta [2] on the oxidation of hydrocarbons and CO,many gold clusters and nanoparticles have been structurally characterized and studied in catalysis. [3,4] Recently,s mall gold clusters have been found to activate the CÀIb ond of iodobenzene in the gas phase [5] and to catalyze reactions usually performed by mononuclear gold complexes. [6] However ,t he actual structures of these clusters have not been determined. In this context, it is important to note that the group of Bertrand reported the synthesis of mixed-valence trinuclear [Au 0 2 Au I ]c lusters which are catalysts for the carbonylation of aliphatic amines under homogeneous conditions. [7] As part of our program on the study of the catalytic activity of well-defined gold(I) clusters, [8] we now report ar eady synthesis of linear [Au 4 ], pentagonal [Au I 4 M I ](M= Cu, Ag), and octagonal [Au 8 ]c omplexes.T he linear [Au 4 ] complex reacts with carbonyl compounds by CÀHf unction-alization to form square-planar complexes.F urthermore,t he pentanuclear complex [Au I 4 Ag I ]h as been found to be an excellent homogeneous catalyst for the carbonylation of amines. Our synthesis started from the dinuclear gold(I) complex 1,w hich is quantitatively prepared by mixing 2,6-bis(diphe-Scheme 1. Synthesis of the [Au 4 ]c omplexes 2 and 3 and the [Au 8 ] complex 4.A= SbF 6 ,B= BF 4 .

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“…33 This work is based on kinetically stable cyclen DO3A type frameworks and initially focused on the self-assembly of mononuclear Tb III and Eu III complexes where the charge neutral Eu III complex contained a free carboxylic acid on the periphery of the complex (Figure 6), free to bind to the cationic Tb III through electrostatic interactions.…”

Section: Self-assembly Of Polynuclear Ln III Containing Architecturesmentioning

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Lanthanides: Supramolecular Chemistry

Kitchen

Gunnlaugsson

2012

Encyclopedia of Inorganic and Bioinorganic Chemistry

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SUMMARYRecent advances in the field of supramolecular lanthanide chemistry are presented with emphasis on their role in the formation of functional self-assembly structures. Such systems are important for future applications in sensing and functional nano-materials, and therefore a small portion of the work from some of the leaders in this field are presented to give an overview of the state of the art to date. We have limited our overview to examples from the literature that have emerged in the last few years. We begin with a short overview of the use of lanthanide complexes and self-assembly structures for use in sensing of biologically important cations and anions and their application in luminescence imaging of bone structures. We then discuss the formation of simple self-assemblies that are formed from the use of pyridyl-based ligands, usually giving rise to the formation of discrete luminescent lanthanide complexes, some of which give rise to chiral emission. The formation of polynuclear lanthanide complexes is then described. Their luminescent and magnetic properties and the use of such ligands in the formation of higher order selfassemblies such as boxes and helicates are discussed. The idea of using mixed f-and d-metal ions in such systems is then presented. We pay particular attention to examples where the self-assembly structures have been analyzed by X-ray crystal structure analysis and by using changes in the luminescent properties to observe their formation in situ. INTRODUCTIONOwing to the unique physical and coordination properties of the lanthanides, they have become important players in the field of supramolecular chemistry. In the past few years, a large number of reviews have been published that deal with the use of the lanthanides in the formation of simple coordination

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Self-assembly between dicarboxylate ions and a binuclear europium complex: formation of stable adducts and heterometallic lanthanide complexes

Abstract: A binuclear lanthanide complex consisting of two lanthanide binding domains linked by a m-xylyl bridging unit forms very stable 1 : 1 adducts with benzene dicarboxylic acids and their derivatives. The complex with isophthalate derivatives is particularly stable.

Cited by 46 publications

References 28 publications

Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb⋅DTMA]³⁺ in Aqueous Solution

Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb⋅DTMA]³⁺ in Aqueous Solution

Heterometallic Complexes Containing Lanthanides

Lanthanides: Supramolecular Chemistry

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Self-assembly between dicarboxylate ions and a binuclear europium complex: formation of stable adducts and heterometallic lanthanide complexes

Abstract: A binuclear lanthanide complex consisting of two lanthanide binding domains linked by a m-xylyl bridging unit forms very stable 1 : 1 adducts with benzene dicarboxylic acids and their derivatives. The complex with isophthalate derivatives is particularly stable.

Cited by 46 publications

References 28 publications

Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb⋅DTMA]3+ in Aqueous Solution

Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb⋅DTMA]3+ in Aqueous Solution

Heterometallic Complexes Containing Lanthanides

Lanthanides: Supramolecular Chemistry

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Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb⋅DTMA]³⁺ in Aqueous Solution

Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb⋅DTMA]³⁺ in Aqueous Solution