Interaction between tetrathiafulvalene carboxylic acid and ytterbium DO3A: solution state self-assembly of a ternary complex which is luminescent in the near IRElectronic supplementary information (ESI) available: cyclic voltammograms of TTF-YbDO3A and YbDO3A. See http://www.rsc.org/suppdata/cc/b2/b204218e/

Faulkner, Stephen; Burton‐Pye, Benjamin P.; Khan, Tahir; Martin, Leigh R.; Wray, Steven D.; Skabara, Peter J.

doi:10.1039/b204218e

Cited by 84 publications

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“…Self-assembled helicates, relying o n thermodynamic stability, have been prepared and studied in great detail. 5, 12-14 We and others have exploited the formation of ternary complexes between kinetically stable lanthanide complexes and simple carboxylates to probe energy transfer, 15 and as a fast and effective means of screening chromophores for use as sensitisers of lanthanide emission. 16, 17 K=aEu2.1:5aEu2.1⋅abold5=γ[Eu2.1:5][Eu2.1]⋅γ[5]=[Eu2.1:5][Eu2.1]⋅[5]…”

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Self-assembly between dicarboxylate ions and binuclear europium complexes: moving to water—pH dependence and effects of buffers

et al. 2013

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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.The nature of the f-electron configurations of the trivalent lanthanide ions results in long lived, high intensity luminescence and strong paramagnetic perturbation of proton resonances as well as highly reduced relaxation times in NMR. Bioassays based on lanthanide chemistry, where the long lived lanthanide centred emission allows for separation of fluorescence background and signal, exploit self-assembly on both the immunology side and to develop the highly emissive lanthanide species that supply the readout for the assay. 1 Lanthanide luminescence is also used in optical imaging, 2-5 where time-gating methodologies can be applied to reduce background noise and detection limit. 6 Gadolinium complexes have been extensively used as MRI contrast agents, 7-10 while bimodal lanthanide based imaging agents have been demonstrated that combine approaches to imaging. 11Self-assembled helicates, relying o n thermodynamic stability, have been prepared and studied in great detail. 5,[12][13][14] We and others have exploited the formation of ternary complexes between kinetically stable lanthanide complexes and simple carboxylates to probe energy transfer, 15 Self-complementary lanthanide complexes of DO3A with benzoate pendent arms exhibit pH-dependent self-association that modulates the luminescence intensity of the lanthanide emission by a combination of water displacement and an increase in of sensitisation efficiency. 18 Such modulation has been used as the basis for lanthanide luminescence sensors, 19-23 a number of which work in aqueous and biological media. 3,[24][25][26] The binding pocket of the binuclear complexes Eu 2 .1-3 consists of the seven-coordinate europium centres and the flat aromatic bridge (Scheme 1). The coordination number of europium is nine, which offers the possibility of both mono-and bi-dentate binding of carboxylates to each europium centre. We have recently shown that isophthalate ions are ideally suited to bind in this binding pocket (Scheme 2), in a study where the association of α, α'-bis(Eu.DO3A)-5-amino-m-xylene (Eu 2 .2) and isophthalate (5) was investigated.Isophthalate is not water-soluble, and we were obliged to use the terbium complex Tb.4 to study assembly processes with Eu 2 .2 in water. 27 In this work, we explore the binding of dinicotinate (6), the simplest water-soluble analogue of isophthalate, with three binuclear lanthanide complexes, and show that small changes in structure and solvation can have a profound impact upon binding. Figure 1 shows the changes in the europium centred luminescence upon titrating bis(Eu.DO3A)-3,5-dimethylpyridine (Eu 2 .1) with 6 in TRIS buffer, maintaining [Eu 2 .1] constant. These dramatic changes, make it...

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Self-assembly between dicarboxylate ions and binuclear europium complexes: moving to water—pH dependence and effects of buffers

et al. 2013

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“…To date, various 3d/4d/5d coordination compounds were built up from TTF-carboxylate ligands [18][19][20][21][22][23][24][25]. Nevertheless, examples with 4f elements are very rare and only concern zero-dimensionnal complexes [26,27]. In this communication, we report the first TTF-based lanthanide coordination polymer.…”

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Slow Magnetic Relaxation in Unprecedented Mono-Dimensional Coordination Polymer of Ytterbium Involving Tetrathiafulvalene-Dicarboxylate Linker

et al. 2016

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“…to the emissive state or must be sensitised via a sequential electron transfer mechanism. 13 Either of these mechanisms can be used to explain the energy transfer process, and Rehm-Weller treatment suggests that both may be feasible in this system. The efficiency of Fo¨rster energy transfer is inversely proportional to the sixth power of the donor-acceptor separation, 14 and the rapid rate constants for energy transfer therefore imply that the observed emission comes from the assembled pseudorotaxane, and that the donor and acceptor are close in space within the system.…”

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Sensitised near infrared emission from lanthanides via anion-templated assembly of d–f heteronuclear [2]pseudorotaxanes

et al. 2006

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Cited by 84 publications

References 20 publications

Self-assembly between dicarboxylate ions and binuclear europium complexes: moving to water—pH dependence and effects of buffers

Self-assembly between dicarboxylate ions and binuclear europium complexes: moving to water—pH dependence and effects of buffers

Slow Magnetic Relaxation in Unprecedented Mono-Dimensional Coordination Polymer of Ytterbium Involving Tetrathiafulvalene-Dicarboxylate Linker

Sensitised near infrared emission from lanthanides via anion-templated assembly of d–f heteronuclear [2]pseudorotaxanes

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