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Fully fluorinated imidodiphosphinate shells for visible- and NIR-emitting lanthanides: hitherto unexpected effects of sensitizer fluorination on lanthanide emission properties

(2007) CHEMISTRY-A EUROPEAN JOURNAL. 13(22). p.6308-6320
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Abstract
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-dipentafluoro-phenylphosphinimidic acid (HF(20)tpip), 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(F(20)tpip)(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 HF(20)tpip and [Gd(F(20)tpip)(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(F(20)tpip)(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(F(20)tpip)(3)], [Er(F(20)tpip)(3)] and [Yb(F(20)tpip)(3)] in deuteurated acetonitrile are 44, 741 and 1111 mu s. The highest value observed for the [Yb(F(20)tpip)(3)] complex is more than half the value of the Yb ion radiative lifetime.
Keywords
lanthanides, ligand design, luminescence, photochemistry, supramolecular chemistry, NEAR-INFRARED LUMINESCENCE, COORDINATION POLYMERS, PHOTOPHYSICAL PROPERTIES, BUILDING-BLOCKS, ENERGY-TRANSFER, TRIPLET-STATE, COMPLEXES, IONS, LIGANDS, EUROPIUM

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Citation

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Chicago
Glover, Peter B, Andrew P Bassett, Peter Nockemann, Benson M Kariuki, Rik Van Deun, and Zoe Pikramenou. 2007. “Fully Fluorinated Imidodiphosphinate Shells for Visible- and NIR-emitting Lanthanides: Hitherto Unexpected Effects of Sensitizer Fluorination on Lanthanide Emission Properties.” Chemistry-a European Journal 13 (22): 6308–6320.
APA
Glover, P. B., Bassett, A. P., Nockemann, P., Kariuki, B. M., Van Deun, R., & Pikramenou, Z. (2007). Fully fluorinated imidodiphosphinate shells for visible- and NIR-emitting lanthanides: hitherto unexpected effects of sensitizer fluorination on lanthanide emission properties. CHEMISTRY-A EUROPEAN JOURNAL, 13(22), 6308–6320.
Vancouver
1.
Glover PB, Bassett AP, Nockemann P, Kariuki BM, Van Deun R, Pikramenou Z. Fully fluorinated imidodiphosphinate shells for visible- and NIR-emitting lanthanides: hitherto unexpected effects of sensitizer fluorination on lanthanide emission properties. CHEMISTRY-A EUROPEAN JOURNAL. 2007;13(22):6308–20.
MLA
Glover, Peter B, Andrew P Bassett, Peter Nockemann, et al. “Fully Fluorinated Imidodiphosphinate Shells for Visible- and NIR-emitting Lanthanides: Hitherto Unexpected Effects of Sensitizer Fluorination on Lanthanide Emission Properties.” CHEMISTRY-A EUROPEAN JOURNAL 13.22 (2007): 6308–6320. Print.
@article{1190140,
  abstract     = {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-dipentafluoro-phenylphosphinimidic acid (HF(20)tpip), 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(F(20)tpip)(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 HF(20)tpip and [Gd(F(20)tpip)(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(F(20)tpip)(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(F(20)tpip)(3)], [Er(F(20)tpip)(3)] and [Yb(F(20)tpip)(3)] in deuteurated acetonitrile are 44, 741 and 1111 mu s. The highest value observed for the [Yb(F(20)tpip)(3)] complex is more than half the value of the Yb ion radiative lifetime.},
  author       = {Glover, Peter B and Bassett, Andrew P and Nockemann, Peter and Kariuki, Benson M and Van Deun, Rik and Pikramenou, Zoe},
  issn         = {0947-6539},
  journal      = {CHEMISTRY-A EUROPEAN JOURNAL},
  keyword      = {lanthanides,ligand design,luminescence,photochemistry,supramolecular chemistry,NEAR-INFRARED LUMINESCENCE,COORDINATION POLYMERS,PHOTOPHYSICAL PROPERTIES,BUILDING-BLOCKS,ENERGY-TRANSFER,TRIPLET-STATE,COMPLEXES,IONS,LIGANDS,EUROPIUM},
  language     = {eng},
  number       = {22},
  pages        = {6308--6320},
  title        = {Fully fluorinated imidodiphosphinate shells for visible- and NIR-emitting lanthanides: hitherto unexpected effects of sensitizer fluorination on lanthanide emission properties},
  url          = {http://dx.doi.org/10.1002/chem.200700087},
  volume       = {13},
  year         = {2007},
}

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