Europium(III) complex with powerful antenna ligands: Interligand interaction

Emelina, T. B.; Kalinovskaya, I. V.; Мирочник, А. Г.

doi:10.1016/j.saa.2018.09.012

Cited by 16 publications

(10 citation statements)

References 25 publications

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“…The energies of singlet states are estimated using the onsets of the absorption edges observed in the reflectance spectra given in Figure a. Following this approach, the first excited singlet of tfa may be located at ≈42100 cm –1 (S 1 ), in good agreement with previous spectroscopic studies of lanthanide trifluoroacetates. − ,, In the case of 4-cpno, the first two excited singlets of 4-cpno appear to be located at 27954 cm –1 (S 1 , n → π*) and 36325 cm –1 (S 2 , π → π*); both values are in excellent agreement with those previously reported for pyridine N -oxide. − The positions of the lowest-lying triplet states (T 1 ) are estimated using the highest-energy edge of the emission bands observed in the phosphorescence spectra shown in Figure b. The spectrum of Gd(tfa) 3 (H 2 O) 3 exhibits two peaks at 23320 and 21858 cm –1 .…”

Section: Resultsmentioning

confidence: 99%

“…This strategy is commonly used in the design and synthesis of mono- and polynuclear luminescent lanthanide complexes . Following this approach, mixed-ligand lanthanide trifluoroacetates featuring 2,2′-bipyridine, ,− 1,10-phenanthroline, ,, diphenylguanidine, tris[3-(2′-pyridyl)pyrazolyl]borate, triphenylphosphine oxide, and hexamethylphosphotriamide have been synthesized. Unfortunately, these studies did not report luminescence quantum yields and sensitization efficiencies.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Structure, and Luminescence of Mixed-Ligand Lanthanide Trifluoroacetates

et al. 2022

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A series of new mixed-ligand lanthanide trifluoroacetates of formula Ln(4-cpno)(tfa)3(H2O)·H2O (Ln = Sm, Eu, Gd, Tb, Dy; 4-cpno = 4-cyanopyridine N-oxide; tfa = trifluoroacetate) is reported. Trifluoroacetates were synthesized as chemically pure polycrystalline solids and their crystal structures were probed using single-crystal and powder X-ray diffraction. Ln(4-cpno)(tfa)3(H2O)·H2O solids make up an isostructural series in which LnO8 polyhedra are bridged by 4-cpno to form edge-sharing dimers. Trifluoroacetato connects these dimers to yield chains whose three-dimensional packing is governed by hydrogen bonds established between 4-cpno, trifluoroacetato, and water. 4-cpno serves as an efficient sensitizer of lanthanide-centered luminescence. UV excitation of its singlet manifold and subsequent energy transfer to the 4f levels of the lanthanides yield orange (Sm), red (Eu), green (Tb), and yellow (Dy) emissions. Sensitization efficiencies reach 81 and 64% for Eu and Tb hybrids, respectively. Tb(4-cpno)(tfa)3(H2O)·H2O displays a quantum yield of 52%, which coupled to the high absorptivity of 4-cpno, makes it a bright-green emitter under 292 nm excitation. Lanthanide trifluoroacetates may therefore serve as hybrid solid-state light emitters provided that adequate sensitizers are identified.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, and Luminescence of Mixed-Ligand Lanthanide Trifluoroacetates

et al. 2022

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“…A similar example of the interligand electron density transfer that influenced the optical and photochemical properties of lanthanide complexes was revealed previously. [ 36 ]…”

Section: Resultsmentioning

confidence: 99%

“…A similar example of the interligand electron density transfer that influenced the optical and photochemical properties of lanthanide complexes was revealed previously. [36] A distinctive feature of the terbium and dysprosium complexes is the appearance of an unusually powerful π-conjugated antenna system formed by phenanthroline molecules in the excited state.…”

Section: Resultsmentioning

confidence: 99%

Thermoluminescent Tb(III) and Dy(III) complexes with redox‐active ligands: experimental and theoretical study

Emelina

Мирочник

2022

Luminescence

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Thermoluminescence and persistent luminescent materials with unique delayed emission have attracted much attention and exhibit great promise in optical information storage. In this manuscript, to reveal the thermoluminescence mechanism, a combined experimental and theoretical study of ternary Ln(NO3)2Acac(Phen)2 complexes, where Ln is Tb(III), Dy(III), Eu(III), Acac is acetylacetonate anion, and Phen is 1,10‐phenanthroline, was carried out. The terbium and dysprosium complexes had thermoluminescence properties, while the europium complex did not. A thermoluminescence mechanism is proposed: the powerful double π‐conjugate phenanthroline system appearance upon photoexcitation, the peculiarities of frontier orbitals, the abnormally small highest occupied molecular orbital–lowest unoccupied molecular orbital gap, and the geometrical changes in the terbium and dysprosium complexes led us to suggest that phenanthroline molecules serve as ‘chemical’ electron traps. Therefore, we succeeded in ‘freezing’ and storing the excited state of complexes I and II indefinitely. The obtained thermoluminescent materials with ‘chemical’ traps of electrons are capable of storing the energy from incident photons and exhibit a great opportunity in optical information storage and anticounterfeiting applications.

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“…However, due to the difficulties with direct sensitization of Ln(III) luminescence organic ligands (L) are usually used to excite lanthanides indirectly mainly by ligands' triplet level [4][5][6][7]. Within the complex of Ln(III)-L, the efficiency of ligand-to-metal energy transfer governs the resulting brightness and, hence, luminescence performance in various applications.…”

Section: Introductionmentioning

confidence: 99%

Phosphineoxide-Chelated Europium(III) Nanoparticles for Ceftriaxone Detection

Zairov¹,

Dovzhenko²,

Terekhova³

et al. 2022

Preprint

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The present work demonstrates the optimization of the ligand structure in the series of bis-phosphine oxide and carbamoylphosphine oxide representatives for efficient coordination of Tb3+ and Eu3+ ions with the formation of the complexes exhibiting high Tb3+- and Eu3+-centered luminescence. The analysis of the stoichiometry and structure of the lanthanide complexes obtained by XRD method reveals the great impact of the bridging group nature between two phosphine oxide moieties on the coordination mode of the ligands with Tb3+ and Eu3+ ions. The bridging imido-group facilitates the deprotonation of imido-bisphosphine oxide ligand followed by the formation of tris-complexes. The spectral and PXRD analysis of the separated colloids indicates that the high stability of the tris-complexes provides their safe conversion into polystyrenesulfonate-stabilized colloids under the solvent exchange method. The red Eu3+-centered luminescence of the tris-complex exhibits the same specificity in the solutions and the colloids. The pronounced luminescent response on the antibiotics ceftriaxone allows to sense the latter in aqueous solutions with the LOD value equal to 0.974 M.

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Europium(III) complex with powerful antenna ligands: Interligand interaction

Cited by 16 publications

References 25 publications

Synthesis, Structure, and Luminescence of Mixed-Ligand Lanthanide Trifluoroacetates

Synthesis, Structure, and Luminescence of Mixed-Ligand Lanthanide Trifluoroacetates

Thermoluminescent Tb(III) and Dy(III) complexes with redox‐active ligands: experimental and theoretical study

Phosphineoxide-Chelated Europium(III) Nanoparticles for Ceftriaxone Detection

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