Controlled assembly of luminescent racks based on heteroleptic dinuclear lanthanide complexes

Castaño-Briones, M. Margarita; Bassett, Andrew P.; Meason, Linette L.; Ashton, Peter R.; Pikramenou, Zoe

doi:10.1039/b412999g

Cited by 15 publications

(7 citation statements)

References 23 publications

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“…Two pendant amide arms provide versatile thiophenol groups for binding to soft metals or forming disulfide bonds. Previously, we have reported lanthanide complexes of functional DTPA-bis(amides) as luminescent sensors, 18 taking part in the self-assembled formation of dinuclear lanthanide complexes, 19 in assembly with platinum moieties, 20 and assembled on luminescent gold nanoparticles. 21 In this paper we introduce an activated thiol approach in the thiol-disulfide exchange chemistry for the solution assembly of LnLn 0 L x 2 macrocycles.…”

Section: ' Introductionmentioning

confidence: 99%

Purely Heterometallic Lanthanide(III) Macrocycles through Controlled Assembly of Disulfide Bonds for Dual Color Emission

et al. 2010

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Lanthanide complexes based on bis(amides) of diethylenetriaminepentaacetic acid with thiol functionalities are modified with 2,2'-dipyridyl disulfide to give activated complexes that can selectively react with thiol-functionalized complexes to form heterometallic lanthanide macrocycles. The preparation and full characterization of the polyaminocarboxylate ligands N,N''-bis[p-thiophenyl(aminocarbonyl)]diethylenetriamine-N,N',N''-triacetic acid (H(3)L(x)) and the activated N,N''-bis[p-(pyridyldithio)[phenyl(aminocarbonyl)]]diethylenetriamine-N,N',N''-triacetic acid (H(3)L(y)) and the complexes LaL(x), NdL(x), SmL(x), EuL(x), GdL(x), DyL(x), TbL(x), ErL(x), and YbL(x) are reported. The luminescence properties of the LnL(x) complexes emitting in the visible (where Ln = Dy(3+), Tb(3+), Eu(3+), and Sm(3+)) are examined by steady-state and time-resolved photoluminescence, and the triplet state energy level of GdL(x) was estimated to be 24 100 cm(-1) from the 0-0 band of the 77 K phosphorescence spectrum. Near-infrared emission was detected for the NdL(x), YbL(x), and ErL(x) complexes, demonstrating the versatility of the thiophenol chromophore. The assembly of purely heterometallic EuTbL(x)(2) macrocycles by reaction of EuL(x) with TbL(y) was followed by UV-vis absorption spectroscopy, monitoring the characteristic absorption peak of pyridyl-2-thione at 353 nm. Analysis of the solution by mass spectrometry reveals the formation of purely heterometallic macrocycle EuTbL(x)(2). This is in contrast with the results obtained by dynamic self-assembly under oxidative conditions, where we observe a statistical mixture of macrocyclic complexes of Eu(2)L(x)(2), Tb(2)L(x)(2), and EuTbL(x)(2). The EuTbL(x)(2) macrocycle displays dual color emission, incorporating the characteristic f-f transitions of Eu(3+) and Tb(3+). Investigation into the time-resolved photophysical properties of EuTbL(x)(2) reveals energy transfer from Tb(3+) to Eu(3+), facilitated by the different conformations of the macrocycle in solution.

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Section: ' Introductionmentioning

confidence: 99%

Purely Heterometallic Lanthanide(III) Macrocycles through Controlled Assembly of Disulfide Bonds for Dual Color Emission

et al. 2010

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“…Lanthanide helices, [1][2][3][4][5] wheels, [6][7][8] starbust shapes, [9] hairpins, [10] racks, [11,12] rotaxanes, [13] squares [14] and other high-dimensional architectures [15][16][17][18][19][20][21] have been prepared. When luminescent lanthanides are introduced into these architectures, new properties can be explored for materials and sensing applications.…”

Section: Introductionmentioning

confidence: 99%

Fully Fluorinated Imidodiphosphinate Shells for Visible‐ and NIR‐Emitting Lanthanides: Hitherto Unexpected Effects of Sensitizer Fluorination on Lanthanide Emission Properties

Glover

Bassett

Nockemann

et al. 2007

Chemistry A European J

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In this paper we demonstrate that the effect of aromatic C--F substitution in ligands does not always abide by conventional wisdom for ligand design to enhance sensitisation for visible lanthanide emission, in contrast with NIR emission for which the same effect coupled with shell formation leads to unprecedented long luminescence lifetimes. We have chosen an imidodiphosphinate ligand, N-{P,P-di(pentafluorophinoyl)}-P,P-dipentafluorophenylphosphinimidic acid (HF20tpip), to form ideal fluorinated shells about all visible- and NIR-emitting lanthanides. The shell, formed by three ligands, comprises twelve fully fluorinated aryl sensitiser groups, yet no-high energy X--H vibrations that quench lanthanide emission. The synthesis, full characterisation including X-ray and NMR analysis as well as the photophysical properties of the emissive complexes [Ln(F20tpip)3], in which Ln=Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, Y, Gd, are reported. The photophysical results contrast previous studies, in which fluorination of alkyl chains tends to lead to more emissive lanthanide complexes for both visible and NIR emission. Analysis of the fluorescence properties of the HF20tpip and [Gd(F20tpip)3] reveals that there is a low-lying state at around 715 nm that is responsible for partially quenching of the signal of the visible emitting lanthanides and we attribute it to a pi-sigma* state. However, all visible emitting lanthanides have long lifetimes and unexpectedly the [Dy(F20tpip)3] complex shows a lifetime of 0.3 ms, indicating that the elimination of high-energy vibrations from the ligand framework is particularly favourable for Dy. The NIR emitting lanthanides show strong emission signals in powder and solution with unprecedented lifetimes. The luminescence lifetimes of [Nd(F20tpip)3], [Er(F20tpip)3] and [Yb(F20tpip)3] in deuteurated acetonitrile are 44, 741 and 1111 micros. The highest value observed for the [Yb(F20tpip)3] complex is more than half the value of the Yb ion radiative lifetime.

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“…[ [21][22][23][24][25] In our previous studies, platinum terpyridyl units. Pt-tpy (tpy = 2,2';6',2"terpyridine), were attached via thiophenol moieties to the DTPA-bisamide but the presence of a thiophenol to terpyridyl charge transfer state in the visible region limited the luminescence properties of the complexes.…”

Section: Introductionmentioning

confidence: 99%

A luminescent europium hairpin for DNA photosensing in the visible, based on trimetallic bis-intercalators

Scarpantonio

Cotton

Giorgio

et al. 2020

Journal of Inorganic Biochemistry

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Controlled assembly of luminescent racks based on heteroleptic dinuclear lanthanide complexes

Abstract: Luminescent lanthanide racks are formed in solution through supramolecular assembly of lanthanide ions with a rigid bis-didentate sensitiser ligand and octadentate aminopolycarboxylate ligands.

Cited by 15 publications

References 23 publications

Purely Heterometallic Lanthanide(III) Macrocycles through Controlled Assembly of Disulfide Bonds for Dual Color Emission

Purely Heterometallic Lanthanide(III) Macrocycles through Controlled Assembly of Disulfide Bonds for Dual Color Emission

Fully Fluorinated Imidodiphosphinate Shells for Visible‐ and NIR‐Emitting Lanthanides: Hitherto Unexpected Effects of Sensitizer Fluorination on Lanthanide Emission Properties

A luminescent europium hairpin for DNA photosensing in the visible, based on trimetallic bis-intercalators

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