Lanthanide complexes with substituted naphtholate ligands: extraordinary bright near-infrared luminescence of ytterbium

Pushkarev, Anatoly P.; Ilichev, V. A.; Balashova, T. V.; Vorozhtsov, D. L.; Burin, M. E.; Kuzyaev, D. M.; Fukin, Georgy K.; Andreev, B. A.; Kryzhkov, D. I.; Yablonskiy, A. N.; Bochkarev, M. N.

doi:10.1007/s11172-013-0051-z

Cited by 22 publications

(26 citation statements)

References 18 publications

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“…Importantly, the data show superior EL characteristics for 38 in comparison to complexes of other rare earth metals. A similar trend was pointed out for all ytterbium phenolates and naphtholates having heterocyclic substituents [10,28,29]. Optimization of the device (ITO/CuPc/NPD/38/BATH/LiF/Al) led to further increase in the radiation intensity up to 3140 µW/cm 2 at 13 V [14].…”

Section: Luminescent Lanthanide Complexessupporting

confidence: 69%

“…Since this spectral region is virtually inaccessible to organic dyes, investigation was focused on the complexes of d and some f metals (mainly trivalent lanthanides including Pr, Nd, Ho, Er, Tm, Yb) emitting in the range from 800 to 3000 nm. In order to produce effective NIR luminophores, a set of complexes of the mentioned metals with C 6 F 5 O [8], q [26,27], mbt [19], OON, SON [28], OON 5Me , OON 6Me [10], NpOON and NpSON [29] ligands were prepared and their PL and EL features were studied. The performance of the most efficient NIR emitting devices based on Nd, Er, Tm and Yb compounds are listed in Table 1.…”

Section: Luminescent Lanthanide Complexesmentioning

confidence: 99%

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Synthesis and luminescence of some rare earth metal complexes

Bochkarev¹,

Pushkarev²

2016

Organic Photonics and Photovoltaics

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Abstract:In the present paper the synthesis, photoand electroluminescent properties of new rare earth metal complexes prepared and studied at the Razuvaev Institute of Organometallic Chemistry during the last decade are reviewed. The obtained compounds give luminescence in UV, visible and NIR regions. The substituted phenolates, naphtholates, mercaptobenzothiazolate, 8-oxyquinolinolate, polyfluorinated alcoholates and chalcogenophosphinates were used as ligands. The synthesis and structure of unusual three-nuclear sulfidenitride clusters of Nd and Dy are described. The new excitation mechanism of ytterbium phenolates and naphtholates, which includes the stage of reversible reduction of Yb to divalent state and oxidation of the ligands in the excitation process, is discussed.

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Section: Luminescent Lanthanide Complexessupporting

confidence: 69%

Section: Luminescent Lanthanide Complexesmentioning

confidence: 99%

Synthesis and luminescence of some rare earth metal complexes

Bochkarev¹,

Pushkarev²

2016

Organic Photonics and Photovoltaics

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“…The energy difference between the ligand 3 ππ* state and the 2 F 5/2 Yb 3+ excited state is approximately 10 454 cm −1 , which should favor an efficient energy transfer 41. 42 In the case of Yb 3+ , energy transfer through a ligand‐to‐metal charge transfer state may also occur 43. 44 Characteristic NIR fluorescent emission was observed from the [Yb(Ae ⋅ HOEt)( L ) 4 ] 2 (Ae + =Na + and Rb + ) assemblies in the λ =900 to 1100 nm region (Figure 4), analogous to the reported [Yb(K ⋅ HOEt)( L ) 4 ] 2 33.…”

Section: Resultsmentioning

confidence: 99%

“…[41,42] In the case of Yb 3 + ,energy transfer through aligand-to-metal chargetransfer state may also occur. [43,44] Characteristic NIR fluorescent emission was observed from the [Yb(Ae·HOEt)(L) 4 ] 2 (Ae + = Na + and [33] Table 1. Selecteds eparations between the two lanthanoid cations (Ln···Ln) within the tetranuclear assemblies, between the lanthanoid centers and the ethanol/n-butanol OH group (Ln···OH), and the average LnÀ Ob ond lengths within the first coordination sphere.…”

Section: Photophysical Properties Of the Nir-emitting Yb 3 + + And Ermentioning

confidence: 99%

Lanthanoid/Alkali Metal β‐Triketonate Assemblies: A Robust Platform for Efficient NIR Emitters

Reid

Stagni

Malicka³

et al. 2015

Chemistry A European J

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The reaction of hydrated lanthanoid chlorides with tribenzoylmethane and an alkali metal hydroxide consistently resulted in the crystallization of neutral tetranuclear assemblies with the general formula [Ln(Ae⋅HOEt)(L)4 ]2 (Ln=Eu(3+) , Er(3+) , Yb(3+) ; Ae=Na(+) , K(+) , Rb(+) ). Analysis of the crystal structures of these species revealed a coordination geometry that varied from a slightly distorted square antiprism to a slightly distorted triangular dodecahedron, with the specific geometrical shape being dependent on the degree of lattice solvation and identity of the alkali metal. The near-infrared (NIR)-emitting assemblies of Yb(3+) and Er(3+) showed remarkably efficient emission, characterized by significantly longer excited-state lifetimes (τobs ≈37-47 μs for Yb(3+) and τobs ≈4-6 μs for Er(3+) ) when compared with the broader family of lanthanoid β-diketonate species, even in the case of perfluorination of the ligands. The Eu(3+) assemblies show bright red emission and a luminescence performance (τobs ≈0.5 ms, ${{\Phi}{{{\rm L}\hfill \atop {\rm Ln}\hfill}}}$≈35-37 %, ηsens ≈68-70 %) more akin to the β-diketonate species. The results highlight that the β-triketonate ligand offers a tunable and facile system for the preparation of efficient NIR emitters without the need for more complicated perfluorination or deuteration synthetic strategies.

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“…13 The key point of this mechanism is intramolecular reduction of Yb 3+ to Yb 2+ owing to ET from the excited anionic ligand (L -)* to Yb 3+ and back ET from Yb 2+ to radical species (L•). 26 The possibility of this transformation is stipulated by the relatively low redox potential of Yb 3+ /Yb 2+ (Ep = -1.18 V View Article Online energy of this system is lower than that of upper-lying 5 D 0 emission level of Eu 3+ . As a result, the Eu 3+ cation in 5 and 6 effectively quenches the ligand luminescence and does not reveal metal-centered emission.…”

Section: Photophysical Propertiesmentioning

confidence: 99%

Luminescent properties of 2-mercaptobenzothiazolates of trivalent lanthanides

Ilichev

Pushkarev

Rumyantcev

et al. 2015

Phys. Chem. Chem. Phys.

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A series of lanthanide complexes (Ln = Nd, Sm, Eu, Gd and Yb) with anionic 2-mercaptobenothiazolate (mbt) ligands were synthesized. Depending on the solvents chosen for the synthesis, Ln(mbt)3(THF)2 and Ln(mbt)3(Et2O) complexes were precipitated from THF and Et2O solutions respectively. The structure of Yb(mbt)3(Et2O) was determined by X-ray analysis. Photophysical properties of the complexes were studied. It was found that under photoexcitation Nd and Yb derivatives exhibit bright metal-centered luminescence in the NIR region while Sm(mbt)3(THF)2 demonstrates intensive visible emission corresponding to (4)G5/2 → (6)HJ (J = 5/2, 7/2, 9/2, 11/2) f-f transitions of Sm(3+) along with NIR emission of moderate intensity. In the case of europium compounds as well as Sm(mbt)3(Et2O) no luminescence was detected. It is assumed that the difference in photoluminescence of Yb and Eu complexes can be explained by an intramolecular electron transfer process, which efficiently proceeds in these compounds.

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Lanthanide complexes with substituted naphtholate ligands: extraordinary bright near-infrared luminescence of ytterbium

Cited by 22 publications

References 18 publications

Synthesis and luminescence of some rare earth metal complexes

Synthesis and luminescence of some rare earth metal complexes

Lanthanoid/Alkali Metal β‐Triketonate Assemblies: A Robust Platform for Efficient NIR Emitters

Luminescent properties of 2-mercaptobenzothiazolates of trivalent lanthanides

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