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

Sørensen, Thomas Just; Tropiano, Manuel; Blackburn, Octavia A.; Tilney, James A.; Kenwright, Alan M.; Faulkner, Stephen

doi:10.1039/c2cc35931f

Cited by 58 publications

(54 citation statements)

References 29 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The tetranuclear trimetallic complex 5, which we reported recently, is closely related to the other structures described here. [18] However, it has no detectable affinity for isophthalate. From this, we may deduce that it is possible to go too far, and that restriction of conformational freedom can actually exclude the preferred binding conformation.…”

Section: Discussionmentioning

confidence: 99%

Using Remote Substituents to Control Solution Structure and Anion Binding in Lanthanide Complexes

Tropiano

Blackburn

Tilney

et al. 2013

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. Abstract: 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.

show abstract

Section: Discussionmentioning

confidence: 99%

Using Remote Substituents to Control Solution Structure and Anion Binding in Lanthanide Complexes

Tropiano

Blackburn

Tilney

et al. 2013

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

show abstract

“…Affinity constants ( K ) between 0 and 10 7 m −1 were observed, and the considerable changes in this system were ascribed to preorganisation of the binuclear complex and removal of “inactive” conformers from the conformational space available within the structure . Exclusion of the “active” conformer in such circumstances effectively precludes binding …”

Section: Introductionmentioning

confidence: 99%

Thermodynamics of Self‐Assembly of Dicarboxylate Ions with Binuclear Lanthanide Complexes

2015

Self Cite

View full text Add to dashboard Cite

Self-assembly of a range of carboxylic acids (benzoic acid, dinicotinic acid, nicotinic acid, and isophthalic acid) with the europium complex of 5-nitro-α,α′-bis(DO3Ayl)-m-xylene (where DO3A is 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid) has been explored to establish the thermodynamics of binding in a range of solvent systems and in a range of aqueous buffer solutions. In this system, profound effects are observed as a consequence of competition by the hydroxide ion, which outcompetes even dinicotinate at high pH. In the case of isophthalate, which binds most strongly, and dinicotinate, both enthalpic and entropic contributions to binding have been identified. The europium complex with 5-nitro-α,α′-bis(DO3Ayl)-m-xylene is found to have a solution structure significantly different from the related europium complex of 5-amino-α,α′-bis(DO3Ayl)-m-xylene. It is found that phosphate binds strongly to the europium complex of the nitro derivate but not to the europium complex of amino derivative. Lactate, citrate, and pyruvate also bind strongly to 5-nitro-α,α′-bis(Eu⋅DO3Ayl)-m-xylene, and it is concluded that the solution structure of this binuclear lanthanide complex is significantly different from that of the amino-substituted complex.

show abstract

“…This approach has the merit of allowing highly defined systems to be prepared, obviating the problem of similarity between lanthanide(III) ions that effectively dooms any approach to specific (as opposed to merely selective) complexation under thermodynamic control. Kinetically inert lanthanide(III) complexes based on the 1,4,7,10‐tetraazacyclododecane‐1,4,7‐triacetic acid (DO3A) motif have been used in copper‐catalysed azide alkyne click, diazotisation, peptide‐coupling and Ugi reactions to form multimetallic and heterometallic lanthanide(III)‐containing architectures …”

Section: Introductionmentioning

confidence: 99%

“…In this manuscript, we demonstrate the use of the Ugi coupling to prepare three heterotrimetallic lanthanide(III)‐containing architectures (Scheme ), with three lanthanide(III) binding pockets covalently attached to a single tertiary amido nitrogen atom. By introducing small variations into the constitution of the architectures, it is possible to investigate the effect of solution structure on the properties of the systems, and we compare the properties of the three architectures in Scheme with those of related heterodimetallic complexes we have recently studied , , , …”

Section: Introductionmentioning

confidence: 99%

Triheterometallic Lanthanide Complexes Prepared from Kinetically Inert Lanthanide Building Blocks

et al. 2017

Self Cite

View full text Add to dashboard Cite

Three molecular structures, each containing three different lanthanide(III) centres, have been prepared by coupling three kinetically inert lanthanide(III) complexes in an Ugi reaction. These 2 kDa molecules were purified by dialysis and characterised by NMR and luminescence techniques. The photophysical properties of these heterotrimetallic complexes were investigated and are discussed by comparison with simpler, but related, heterodimetallic compounds. It was found that an aminonaphthalene unit inhibits the sensitisation of terbium, and that the spatial arrangement of the chromophores and lanthanide(III) centres in these molecules inhibits the efficient sensitisation of europium. We conclude that the intramolecular collisions required for efficient Dexter energy transfer from the sensitiser to the lanthanide(III) centre can be prevented by steric congestion.

show abstract

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

Cited by 58 publications

References 29 publications

Using Remote Substituents to Control Solution Structure and Anion Binding in Lanthanide Complexes

Using Remote Substituents to Control Solution Structure and Anion Binding in Lanthanide Complexes

Thermodynamics of Self‐Assembly of Dicarboxylate Ions with Binuclear Lanthanide Complexes

Triheterometallic Lanthanide Complexes Prepared from Kinetically Inert Lanthanide Building Blocks

Contact Info

Product

Resources

About