Rising Stars in Science and Technology: Luminescent Lanthanide Materials

Bünzli, Jean‐Claude G.

doi:10.1002/ejic.201701201

Cited by 174 publications

(109 citation statements)

References 60 publications

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“…The luminescence properties of the racemic lanthanoid cryptates have already been studied in detail . The three bipyridine units around the lanthanoid ion cause both an efficient shielding from surrounding solvent molecules and an efficient indirect population of the excited state of the lanthanoid via the so‐called antenna effect,– affording lanthanoid complexes with long luminescence lifetimes and good quantum yields …”

Section: Introductionsupporting

confidence: 91%

Circularly Polarised Luminescence in Enantiopure Samarium and Europium Cryptates

Kreidt

Arrico

Zinna

et al. 2018

Chemistry A European J

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Circularly polarised luminescence (CPL) is a chiroptical phenomenon gaining more and more attention, as the availability of the necessary spectrometers is getting better and first applications in bioimaging or for the preparation of OLEDs (organic light emitting diodes) are coming within range. Until now most examples of distinctly CPL-active compounds were europium and terbium complexes though theoretically the electronic structure of samarium should be as suitable as the one of terbium. This discrepancy can be accounted for by the high susceptibility of samarium to non-radiative deactivation processes. The aim of this study was to strategically circumvent this difficulty by the use of a ligand scaffold which has already proven to efficiently suppress these processes, namely the cryptates. The prepared partly deuterated samarium and europium complexes exhibit distinct circularly polarised luminescence with dissymmetry factors up to g =+0.13 (Sm ) or g =-0.19 (Eu ).

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Section: Introductionsupporting

confidence: 91%

Circularly Polarised Luminescence in Enantiopure Samarium and Europium Cryptates

Kreidt

Arrico

Zinna

et al. 2018

Chemistry A European J

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“…Lanthanide‐based photonic devices are finding numerous applications in our daily life, such as phosphors, lasers, or luminescent bioassays . The ability to control the photon flux in Ln devices is of upmost importance to funnel the energy at the expected outcome level, such as for downshifting materials applied to the optimization of solar cells or for efficient biolabeling that targets the optical biological window .…”

Section: Introductionmentioning

confidence: 99%

Energy Transfer in Supramolecular Heteronuclear Lanthanide Dimers and Application to Fluoride Sensing in Water

Nonat

Liu

Jeannin

et al. 2018

Chemistry A European J

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In the presence of fluoride anions, [LnL(H O)] complexes, based on the coordination of a lanthanide (Ln) cation into the cavity of a C symmetrical cyclen-based ligand (L), self-assemble in water to form [(LnL) F] dimers. The crystal structures of the Yb hydrated monomer and of the fluorinated dimer are reported and analyzed to unravel the impact of the cumulative effect of weak hydrogen bonding and aromatic stacking interactions in the supramolecular assembly. The assembly is stable over a broad range of pH 3-8. A combination of equimolar amounts of Eu and Tb complexes led to a quasistatistical mixture of homo- and heterodimers, as observed by using electrospray mass spectrometry. In the heterodimers, selective excitation into the F → D absorption band of the Tb center at λ=488 nm allowed the observation of a Tb-to-Eu downshifting energy transfer, not observed in the absence of fluoride ions. Analysis of the excited-state lifetimes of the dimers within the frame of the Förster theory of energy transfer showed the transfer to have an efficiency of 34 %, with a corresponding Förster radius of 4.1 Å; thereby, unraveling the short Ln-Ln distance as a crucial parameter of the energy-transfer process. By using equimolar mixtures of the Tb and Eu complexes, the energy-transfer phenomenon was used for a ratiometric sensing of fluoride anions in water with a detection limit of 17.7 nm.

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“…Trivalent lanthanide ions present exceptional luminescence properties, ranging from the UV/Visible to the near‐infrared regions, and find major technological applications in lasers, telecommunications, displays, lighting, pressure sensors, security inks and marking, barcoding, luminescent thermometry, bioimaging, and immunoassays . Here, photoluminescent materials were obtained by replacing 10 % of the optically silent Y 3+ , used as a diluting element, by Eu 3+ and Tb 3+ for visible emission, and by Yb 3+ and Er 3+ for near‐infrared emission.…”

Section: Resultsmentioning

confidence: 99%

Rare‐Earth Germanate Visible, Near‐Infrared, and Up‐Conversion Emitters

et al. 2018

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The hydrothermal synthesis and structural characterization of new trivalent rare-earth germanates, Na 4 [(Y 1-a Ln a ) 2 -Ge 4 O 13 ] (Ln = Eu, Tb, or Yb and Er; a = 0.05, 0.1) and Na 4 [(Yb 0.9 Er 0.1 ) 2 Ge 4 O 13 ] are reported. The structure of these solids was solved by single-crystal X-ray diffraction (150 K). The materials crystallize in the orthorhombic non-centrosymmetric Pna2 1 space group, and exhibit a framework comprising unprecedented anionic tetrameric [Ge 4 O 13 ] 10units, tetrameric units of {GeO 4 } tetrahedra, and isolated dimeric units encom- [a] 2444 passing two distinct distorted {REO 6 } octahedra. These rareearth germanates feature interesting photoluminescence properties in the visible and near-infrared spectral regions. Eu 3+ photoluminescence confirms the presence of two distinct rareearth sites. Energy transfer between the latter sites is shown for the Yb 3+ /Er 3+ pair, both displaying significant near-infrared emission. Isomorphous Na 4 [(Yb 0.9 Er 0.1 ) 2 Ge 4 O 13 ] features upconversion emission, an unusual property among rare-earth crystalline germanates.dra. [5] Xu and collaborators, in 2012, studied the effect of pressure on the luminescence properties of both NaEuGeO 4 , [6] a material bearing {EuO 6 } octahedral linear chains and isolated {GeO 4 } tetrahedra, and NaEu 3 (GeO 4 ) 2 (OH) 2 , [7] which features sixmembered ring channels of {EuO 6 } octahedra. The luminescence of NaLnGeO 4 (Ln = Sm, Eu, Gd, Tb) has been further investigated by Yeon et al. [8] The tunable emission capability of K 3 [Tb x Eu 1-x Ge 3 O 8 (OH) 2 ] (x = 1, 0.88, 0.67, 0) [9] and the Gd 3+ -to-Tb 3+ energy-transfer process in K 3 [Gd 1-x Tb x Ge 3 O 8 (OH) 2 ] (x = 0, 0.3, 0.1, 1), [10] a family of layered compounds structurally analogous to K 3 LnSi 3 O 8 (OH) 2 (Ln = Y 3+ , Eu 3+ , Tb 3+ , Er 3+ ), [2a] have also been discussed.Here, we report a new RE germanate system, Na 4 [(Y 1-a Ln a ) 2 -Ge 4 O 13 ] (Ln = Eu, Tb, or Yb and Er; a = 0.05, 0.1), whose crystal structure consists of {GeO 4 } tetrahedra forming unprecedented tetrameric [Ge 4 O 13 ] 10units, isolated dimeric units comprising two distinct distorted {REO 6 } octahedral, and charge-balancing Na + cations. These materials have been prepared under mild hydrothermal conditions and present significant luminescence properties in the visible and near-infrared spectral regions. Upconversion emission is also demonstrated with the isomorphic compound Na 4 [(Yb 0.9 Er 0.1 ) 2 Ge 4 O 13 ]. Results and Discussion Crystal Structure DescriptionNa 4 [(Y 0.95 Eu 0.05 ) 2 Ge 4 O 13 ] (1) was isolated as single crystals suitable for X-ray diffraction (see Exp. Sect.), crystallizing in the orthorhombic non-centrosymmetric Pna2 1 space group (Table 1), with two crystallographically distinct RE centers in the asymmetric unit (Figure 1). An unrestrained refinement of the crystal structure for the rates of occupancy of the mixed Y 3+Eur.

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Rising Stars in Science and Technology: Luminescent Lanthanide Materials

Cited by 174 publications

References 60 publications

Circularly Polarised Luminescence in Enantiopure Samarium and Europium Cryptates

Circularly Polarised Luminescence in Enantiopure Samarium and Europium Cryptates

Energy Transfer in Supramolecular Heteronuclear Lanthanide Dimers and Application to Fluoride Sensing in Water

Rare‐Earth Germanate Visible, Near‐Infrared, and Up‐Conversion Emitters

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