Imidodiphosphinate ligands as antenna units in luminescent lanthanide complexes

Magennis, Steven W.; Parsons, Simon; Pikramenou, Zoe; Corval, A.; Woollins, J. Derek

doi:10.1039/a808046a

Cited by 81 publications

(49 citation statements)

References 13 publications

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“…[12] The unit cells revealed two types of symmetry around the metal: trigonal prismatic and distorted octahedral. We noticed a short van der Waals contact of a water molecule with the metal centre in the trigonal prismatic structure.…”

Section: Resultsmentioning

confidence: 99%

“…A similar effect was previously observed for the Eu III and Tb III complexes. [12] The observed lifetime reductions correspond to an increase in the decay rate for the complexes of 640 (Eu 3 ), 350 (Tb 3 ), % 10 000 (Sm 3 ) and % 2000 s À1 (Dy 3 ). The conformational freedom of the complexes in solution allows the approach and coordination of a water molecule which can lead to such a decrease.…”

Section: ] [Sm(tpip) 3 ] and [Eu(tpip) 3 ] In Ch 3 Cn (Monitor-mentioning

confidence: 99%

“…A preliminary report of our work with tetraphenylimidodiphosphinate [12] introduced tpip as a new antenna ligand for europium and terbium ions to give highly luminescent, sixcoordinate [Ln(tpip) 3 ] complexes. This article gives a full account of the preparation and identification of complexes of tpip with Ln 3 ions that emit in the visible range (i.e., Ln Sm, Eu, Tb, Dy), as well as the photophysical studies of these complexes in solution and in the solid state.…”

Section: Introductionmentioning

confidence: 99%

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Assembly of Hydrophobic Shells and Shields around Lanthanides

2002

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Die selektive Spaltung von aktivierter Caspase‐8 wurde durch eine photofunktionalisierte Caspase‐3 imitiert, die an bestimmten Positionen der Peptidkette 2‐Nitrophenylglycin(Npg)‐Reste trägt (siehe Bild). Die Aktivität dieser Caspase‐3 wurde durch Bestrahlung mit sichtbarem Licht induziert, die selbständige Spaltung von Caspase‐3 durch den positionsspezifischen Einbau von Npg hingegen supprimiert.

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Section: Resultsmentioning

confidence: 99%

Section: ] [Sm(tpip) 3 ] and [Eu(tpip) 3 ] In Ch 3 Cn (Monitor-mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Assembly of Hydrophobic Shells and Shields around Lanthanides

2002

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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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“…The solution was filtered under N 2 and the benzene removed at reduced pressure giving a thick brown liquid. The crude product was purified by distillation at 0.1 Torr with the desired fraction coming over at 100-104 8C to yield the desired product as a thick golden oil (4.35 g, 9.8 mmol, 54 %) 31. P{ 1 H} NMR (121 MHz, CDCl 3 ): d = 12.8 ppm (quint, 3 J (P,F) = 36 Hz); 19 F{ 1 H} NMR (282 MHz,…”

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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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163

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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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Imidodiphosphinate ligands as antenna units in luminescent lanthanide complexes

Cited by 81 publications

References 13 publications

Assembly of Hydrophobic Shells and Shields around Lanthanides

Assembly of Hydrophobic Shells and Shields around Lanthanides

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

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

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