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

Glover, Peter B.; Bassett, Andrew P.; Nockemann, Peter; Kariuki, Benson M.; Deun, Rik Van; Pikramenou, Zoe

doi:10.1002/chem.200700087

Cited by 168 publications

(95 citation statements)

References 63 publications

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“…As a result, the luminescence exhibited by these ions has high colorimetric purity, which explains their application in, for example, lighting, imaging, and lasers. [53,[55][56][57] The trivalent europium ion in particular offers the possibility to probe the local symmetry in its first coordination sphere, because of its nondegenerate L J multiplets. By studying the fine-structure in the luminescence spectrum, one can distinguish between several noncentrosymmetric crystallographic point groups.…”

Section: Imide ([Hbet]a C H T U N G T R E N N U N G [Tf 2 N]) Is Ablementioning

confidence: 99%

Speciation of Rare‐Earth Metal Complexes in Ionic Liquids: A Multiple‐Technique Approach

Nockemann

Thijs

Lunstroot

et al. 2009

Chemistry A European J

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The dissolution process of metal complexes in ionic liquids was investigated by a multiple-technique approach to reveal the solvate species of the metal in solution. The task-specific ionic liquid betainium bis(trifluoromethylsulfonyl)imide ([Hbet][Tf(2)N]) is able to dissolve stoichiometric amounts of the oxides of the rare-earth elements. The crystal structures of the compounds [Eu(2)(bet)(8)(H(2)O)(4)][Tf(2)N](6), [Eu(2)(bet)(8)(H(2)O)(2)][Tf(2)N](6) x 2 H(2)O, and [Y(2)(bet)(6)(H(2)O)(4)][Tf(2)N](6) were found to consist of dimers. These rare-earth complexes are well soluble in the ionic liquids [Hbet][Tf(2)N] and [C(4)mim][Tf(2)N] (C(4)mim = 1-butyl-3-methylimidazolium). The speciation of the metal complexes after dissolution in these ionic liquids was investigated by luminescence spectroscopy, (1)H, (13)C, and (89)Y NMR spectroscopy, and by the synchrotron techniques EXAFS (extended X-ray absorption fine structure) and HEXS (high-energy X-ray scattering). The combination of these complementary analytical techniques reveals that the cationic dimers decompose into monomers after dissolution of the complexes in the ionic liquids. Deeper insight into the solution processes of metal compounds is desirable for applications of ionic liquids in the field of electrochemistry, catalysis, and materials chemistry.

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Section: Imide ([Hbet]a C H T U N G T R E N N U N G [Tf 2 N]) Is Ablementioning

confidence: 99%

Speciation of Rare‐Earth Metal Complexes in Ionic Liquids: A Multiple‐Technique Approach

Nockemann

Thijs

Lunstroot

et al. 2009

Chemistry A European J

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“…Moreover, the ligand shell around the luminescent ion is made tight, hydrophobic and bulky (Fig. 7), in order to keep any diffusion quenchers (such as water molecules) at a distance [28,29]. An open challenge is to combine this ion-protecting architecture with the integration of an efficient and visible-light absorbing sensitiser at close proximity of the ion.…”

Section: +mentioning

confidence: 98%

“…The experimentally determined luminescence quantum yield of this complex reaches a record value of 3%, which is obviously low compared to lanthanide ions in glasses and crystals or organic dyes in solution whose quantum yields can often exceed 50%. A recent, supplementary strategy for maintaining NIR luminescence is the encapsulation of the ions in aromatic shells, which rigourously prevents quenching solvent molecules from approaching the lanthanide ion [28,29]. [23,24] contains a carbostyril sensitiser, excited at 320 nm.…”

Section: Neodymium(iii) Erbium(iii) and Ytterbium(iii) Complexesmentioning

confidence: 99%

Near-Infrared Luminescent Labels and Probes Based on Lanthanide Ions and Their Potential for Applications in Bioanalytical Detection and Imaging

Werts

2010

Lanthanide Luminescence

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The use of near-infrared (NIR) light in bioanalytical detection and biological imaging presents certain advantages over UV-visible light in terms of penetration depth, reduction of background signals and decreased phototoxicity. Under suitable conditions, complexes of ytterbium(III)-, neodymium(III)-and erbium (III)-containing organic chromophores may display relatively bright NIR luminescence upon excitation with visible light. This contrasts with the more commonly studied visibly luminescent europium(III) and terbium(III) complexes, which generally need UV or blue light for excitation. We discuss the current knowledge on NIR luminescence of lanthanide complexes (including holmium(III), praseodymium(III) and thulium(III)) in solution. It is suggested that among the NIR luminescent lanthanide complexes, ytterbium(III) complexes are likely to be the most promising candidates for biophotonic applications. The study of NIR luminescence and its application in bioanalytical detection are enabled by progress in detector and light source technology, which are also addressed. Recent developments in lanthanide-based NIR luminescent materials, including complexes and doped nanoparticles, are discussed in the light of their potential for bioanalytical application.

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“…While the improved quantum yield of Yb III complexes when compared to other NIR emitters favours their use for bioimaging applications, there has also been significant interest [4,5,6] in the sensitized emission from other 4f metals such as Ln = Nd, Ho, Pr and Er which have well recognised applications as solid state laser materials [7] (eg. Nd ~ 1.06 μm, Ho ~ 2.09 μm), and in telecommunications (eg.…”

Section: 2-hopo Complexes Of Near Infra-red (Nir) Emitting Lanthanimentioning

confidence: 99%

3‐Hydroxypyridin‐2‐one Complexes of Near‐Infrared (NIR) Emitting Lanthanides: Sensitization of Holmium(III) and Praseodymium(III) in Aqueous Solution

Moore

Szigethy

et al. 2008

Angewandte Chemie

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There is a growing interest in Near Infra-Red (NIR) emission originating from organic complexes of Ln III cations. [1,2] As a major impetus, biological tissues are considerably more transparent at these low energy wavelengths when compared to visible radiation, which facilitates deeper penetration of incident and emitted light. [3] Furthermore, the long luminescence lifetimes of Ln III complexes (eg.Yb III , τ rad ~ 1 ms) when compared to typical organic molecules can be utilized to vastly improve signal to noise ratios by employing time-gating techniques. While the improved quantum yield of Yb III complexes when compared to other NIR emitters favours their use for bioimaging applications, there has also been significant interest [4,5,6] in the sensitized emission from other 4f metals such as Ln = Nd, Ho, Pr and Er which have well recognised applications as solid state laser materials [7] (eg. Nd ~ 1.06 μm, Ho ~ 2.09 μm), and in telecommunications (eg. Er ~ 1.54 μm) where they can be used for amplification of optical signals.[8]As a result of their weak (Laporte forbidden) f-f absorptions, the direct excitation of Ln III cations is inefficient, and sensitization of the metal emission is more effectively achieved using the so-called antenna effect. [1] We have previously examined [9] the properties of several Eu III complexes which feature 1-hydroxypyridin-2-one ( Fig. 1) as the light harvesting chromophore. While the 1,2-HOPO isomer was found to strongly sensitize Eu III , we noted the analogous Me-3,2-HOPO isomer does not, which prompted further investigation of the properties of this chromophore with other metals. The synthesis of the 5LIO-Me-3,2-HOPO ligand has been previously reported. [10,11] Our initial in situ screening of this ligand with Pr III , Ho III and Er III revealed sensitized emission in the NIR region only for the former two metal cations. As such, the corresponding Ln III complexes (Ln = Ho, Pr) were then prepared using well established methodologies (see experimental) and the desired compounds were obtained in analytically pure form as the charge neutral ML 2 H complexes. Single crystals [12] of Na[Ho(5LIO-Me-3,2-HOPO) 2 ] suitable for X-ray analysis were also grown from a 5 % aqueous 1:1 (v/v) DMF:MeOH solution diffused with diethyl ether, and the resulting X-ray structure, which was collected at the Advanced Light Source (ALS, Beamline 11.3.1) at Lawrence Berkeley National Laboratory (LBNL), is shown in Fig. 2. This compound crystallizes in the triclinic space group, P⎯1, with a single independent complex molecule in the asymmetric unit, together with one molecule of co-crystallized solvent DMF. Notably, the crystal structure of Na[Ho(5LIO-Me-3,2-HOPO) 2 ] is very similar to that reported [11] for the analogous Ce IV complex, and also the Ln III complexes formed with the 5LIO-1,2-HOPO ligand. [9] As expected, the Ho III atom is coordinated by eight oxygen atoms of the two 5LIO-Me-3,2-HOPO ligands in a sandwich-like structure (Fig. 2), and the average Ho-O bond lengths are 2.36 Å. The Ho-O...

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

Cited by 168 publications

References 63 publications

Speciation of Rare‐Earth Metal Complexes in Ionic Liquids: A Multiple‐Technique Approach

Speciation of Rare‐Earth Metal Complexes in Ionic Liquids: A Multiple‐Technique Approach

Near-Infrared Luminescent Labels and Probes Based on Lanthanide Ions and Their Potential for Applications in Bioanalytical Detection and Imaging

3‐Hydroxypyridin‐2‐one Complexes of Near‐Infrared (NIR) Emitting Lanthanides: Sensitization of Holmium(III) and Praseodymium(III) in Aqueous Solution

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