Crown ether lanthanide complexes as building blocks for luminescent ternary complexes

Magennis, Steven W.; Craig, James S.; Gardner, A; Fucassi, Flavia; Cragg, Peter J.; Robertson, Neil; Parsons, Simon; Pikramenou, Zoe

doi:10.1016/s0277-5387(02)01405-5

Cited by 27 publications

(16 citation statements)

References 37 publications

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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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168

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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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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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168

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“…13,14 We have been interested in the delivery of nanoparticles in cells using lanthanide luminescent and MRI active probes for imaging. 15 We have previously developed lanthanide [16][17][18] and transition metal complexes 19 with surface-active groups for attachment to nanoparticles and surfaces. In this manuscript we wish to introduce nanoparticle functionalisation with peptides bearing dithiol anchoring points and their binding to lanthanide ions.…”

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Peptide coated gold nanoparticles that bind lanthanide ions

Savage¹,

Pikramenou²

2011

Chem. Commun.

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“…Yaftian et al reported the separation of thorium, lanthanium and europium ions by 2-nitrobenzo-18-crown-6 as a selective masking agent. 16 In addition, the solid state structures of lanthanide complexes of monoaza crown ether 17 and diaza crown ether 18 have also been documented. Umetani et al reported an improved extraction-separation of lanthanides and alkali earth ions by acidic extractants, using 18-crown-6 and some sulfonated crown ethers in the aqueous phase.…”

Section: Introductionmentioning

confidence: 99%

Solvent Extraction, Preconcentration and Determination of Thorium with Monoaza 18-Crown-6 Derivative

Dolak

Karakaplan²,

Ziyadanogullar³

et al. 2011

Bulletin of the Korean Chemical Society

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A solvent extraction separation, preconcentration and determination of thorium with a new crown, 2-ethyl-Nbenzyl-4,7,10,13,16-pentaoxa-1-azacyclooctadecane (MACE), is described in the study. The amount of thorium in the aqueous phase and organic phase was determined by Inductively Coupled Plasma-Optical Emission Spectroscopy and Ultraviolet-Visible, respectively. Thorium loaded organic phase was quantitatively stripped in a stage by using 1.0 M HNO 3 . Thorium was effectively extracted with MACE in the pH range of 6-7 to produce a 3:2 complex ratio in the chloroform. A highly sensitive and rapid spectrophotometric method was described for determination of trace amounts of thorium with MACE. The effective molar absorption coefficient at 281 nm is 1.98 × 10 3 mol −1 cm −1 , and the system complies with Beer's law in the range from 0.464 to 2.32 µg mL −1 of thorium. Thorium was also determined in standard and environmental samples.

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Crown ether lanthanide complexes as building blocks for luminescent ternary complexes

Cited by 27 publications

References 37 publications

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

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

Peptide coated gold nanoparticles that bind lanthanide ions

Solvent Extraction, Preconcentration and Determination of Thorium with Monoaza 18-Crown-6 Derivative

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