scholarly journals Об экспериментальном определении параметров интенсивности 4f-4f-переходов по спектрам излучения соединений европия (III)

2022 ◽  
Vol 130 (1) ◽  
pp. 207
Author(s):  
Lucca Blois ◽  
Albano N. Carneiro Neto ◽  
Ricardo L. Longo ◽  
Israel F. Costa ◽  
Tiago B. Paolini ◽  
...  
Keyword(s):  
Unique Feature ◽  
Photon Counting ◽  
Emission Spectra ◽  
Lanthanide Ions ◽  
Quantum Yields ◽  
Correction Factors ◽  
Intensity Parameters ◽  
Trivalent Lanthanide ◽  
Integrated Intensity

Eu3+ complexes and specially β-diketonate compounds are well known and studied in several areas due to their luminescence properties, such as sensors and lightning devices. A unique feature of the Eu3+ ion is the experimental determination of the 4f-4f intensity parameters Ωλ directly from the emission spectrum. The equations for determining Ωλ from the emission spectra are different for the detection of emitted power compared to modern equipment that detects photons per second. It is shown that the differences between Ωλ determined by misusing the equations are sizable for Ω4 (ca. 15.5%) for several Eu3+β-diketonate complexes and leads to differences of ca. 5% in the intrinsic quantum yields Q_Ln^Ln. Due to the unique features of trivalent lanthanide ions, such as the shielding of 4f-electrons, which lead to small covalency and crystal field effects, a linear correlation was observed between Ωλ obtained using the emitted power and photon counting equations. We stress that care should be exercised with the type of detection should be taken and provide the correction factors for the intensity parameters. In addition, we suggest that the integrated intensity (proportional to the areas of the emission band) and the centroid (or barycenter) of the transition for obtaining Ωλ should be determined in the properly Jacobian-transformed spectrum in wavenumbers (or energy). Due to the small widths of the emission bands of typical 4f-4f transitions, the areas and centroids of the bands do not depend on the transformation within the experimental uncertainties. These assessments are relevant because they validate previously determined Ωλ without the proper spectral transformation.

scholarly journals The Temperature Dependence of Fundamental Photophysical Properties of [Eu(MeOH-d4)9]3+ Solvates and [Eu.DOTA(MeOH-d4)]- Complexes

2021 ◽  
Author(s):  
Nicolaj Kofod ◽  
Lea Gundorff Nielsen ◽  
Thomas Just Sørensen
Keyword(s):  
Transition Probabilities ◽  
Photophysical Properties ◽  
Transition Probability ◽  
Energy Levels ◽  
Emission Spectra ◽  
Lanthanide Ions ◽  
Quantum Yields ◽  
Luminescence Spectra ◽  
Absorption Cross ◽  
Apparent Lack

The trivalent lanthanide ions show optical transitions between energy levels within the 4f shell. All these transitions are formally forbidden according to the quantum mechanical selection rules used in molecular photophysics. Nevertheless, highly luminescent complexes can be achieved, and terbium(iii) and europium(iii) ions are particularly efficient emitters. This report started when an apparent lack of data in the literature led us to revisit the fundamental photophysics of europium(iii). The photophysical properties of two complexes – [Eu.DOTA(MeOH-d4)]- and [Eu(MeOH-d4)9]3+ – were investigated in deuterated methanol at five different temperatures. Absorption spectra showed decreased absorption cross sections as the temperature was increased. Luminescence spectra and time-resolved emission decay profiles showed a decrease in intensity and lifetime as a temperature was increased. Having corrected the emission spectra for the actual number of absorbed photons and differences in non-radiative pathways, the relative emission probability was revealed. These were found to increase with increasing temperature. The transition probability for luminescence was shown to increase with temperature, while the transition probability for light absorption decreased. The changes in transition probabilities were correlated to a change in the symmetry of the absorber or emitter, with an average increase in symmetry lowering absorption cross section and access to more asymmetric structures increasing the emission rate constant. Determining luminescence quantum yields and the Einstein coefficient for spontaneous emission allowed us to conclude that lowering symmetry increases both. Further, it was found that collisional self-quenching is an issue for lanthanide luminescence, when high concentrations are used. Finally, detailed analysis revealed results that show the so-called ‘Werts’ method’ for calculating radiative lifetimes and intrinsic quantum yields are based on assumption that does not hold for the two systems investigated here. We conclude that we are lacking a good theoretical description of the intraconfigurational f-f transition, and that there are still aspects of fundamental lanthanide photophysics to be explored.<br>

Fluorometric Properties of N-Methyltetraphenylporphine and Several Derivatives: Evaluation as Standards for Determination of Chlorophyll Concentrations

1982 ◽  
Vol 36 (4) ◽  
pp. 430-435 ◽  
Author(s):  
David K. Lavallee ◽  
Thomas J. McDonough ◽  
Lisa Cioffi
Keyword(s):  
Chlorophyll A ◽  
Organic Solvents ◽  
Fluorescence Spectra ◽  
Emission Spectra ◽  
Quantum Yields ◽  
Polar Organic Solvents ◽  
Solvent Systems ◽  
Nonpolar Organic ◽  
Chlorophyll Concentrations

As part of an ongoing study of the chemistry and properties of N-methylporphyrins and their metal complexes, we have observed that the excitation and emission spectra of N-methyltetraphenylporphyrin and N-methyltetra( p-sulfophenyl)porphyrin and their zinc complexes closely resemble corresponding spectra of chlorophyll a. We have characterized fluorescence spectra for these species in a variety of solvents commonly used for quantitative determination of chlorophylls. Quantum yields for the N-methylporphyrins are lower by approximately a factor of 10 than yields for chlorophyll a in such solvents as acetone, ethanol, and mixed aqueous/organic solvent systems. The yields are quite sufficient, however, for these species to be used as fluorescence standards. Solution of N-methylporphyrins are stable and the compounds can be inexpensively synthesized in high purity. The tetra( p-sulfophenyl) species are soluble in aqueous and highly polar organic solvents, whereas the tetraphenyl species are soluble in nonpolar organic solvents.

scholarly journals Self-referenced method for the Judd–Ofelt parametrisation of the Eu3+ excitation spectrum

2022 ◽  
Vol 12 (1) ◽  
Author(s):  
Aleksandar Ćirić ◽  
Łukasz Marciniak ◽  
Miroslav D. Dramićanin
Keyword(s):  
Excitation Spectrum ◽  
Web Application ◽  
Lanthanide Ions ◽  
Excitation Spectra ◽  
Research Papers ◽  
Intensity Parameters ◽  
Integrated Intensity ◽  
Integrated Intensities ◽  
User Friendly ◽  
Published Research

AbstractJudd–Ofelt theory is a cornerstone of lanthanides’ spectroscopy given that it describes 4fn emissions and absorptions of lanthanide ions using only three intensity parameters. A self-referenced technique for computing Judd–Ofelt intensity parameters from the excitation spectra of Eu3+-activated luminescent materials is presented in this study along with an explanation of the parametrisation procedure and free user-friendly web application. It uses the integrated intensities of the 7F0 → 5D2, 7F0 → 5D4, and 7F0 → 5L6 transitions in the excitation spectrum for estimation and the integrated intensity of the 7F0 → 5D1 magnetic dipole transition for calibration. This approach facilitates an effortless derivation of the Ω6 intensity parameter, which is challenging to compute precisely by Krupke’s parametrisation of the emission spectrum and, therefore, often omitted in published research papers. Compared to the parametrisation of absorption spectra, the described method is more accurate, can be applied to any material form, and requires a single excitation spectrum.

Ab initio calculation of energy levels of trivalent lanthanide ions

2018 ◽  
Vol 20 (21) ◽  
pp. 14564-14577 ◽  
Author(s):  
Alexandra Ya. Freidzon ◽  
Ilia A. Kurbatov ◽  
Vitaliy I. Vovna
Keyword(s):  
Ab Initio ◽  
Ab Initio Calculation ◽  
Lanthanide Complexes ◽  
Energy Levels ◽  
Emission Spectra ◽  
Lanthanide Ions ◽  
Computational Scheme ◽  
Absorption And Emission ◽  
Absorption And Emission Spectra ◽  
Trivalent Lanthanide

A fully ab initio computational scheme employing CASSCF/XMCQDPT2/SO-CASSCF for the absorption and emission spectra of trivalent lanthanide complexes is presented.

scholarly journals Single-Ion Magnet and Photoluminescence Properties of Lanthanide(III) Coordination Polymers Based on Pyrimidine-4,6-Dicarboxylate

2021 ◽  
Vol 7 (1) ◽  
pp. 8
Author(s):  
Oier Pajuelo-Corral ◽  
Jose Angel García ◽  
Oscar Castillo ◽  
Antonio Luque ◽  
Antonio Rodríguez-Diéguez ◽  
...  
Keyword(s):  
Coordination Polymers ◽  
Single Molecule ◽  
Visible Region ◽  
Emission Spectra ◽  
Lanthanide Ions ◽  
Quantum Yields ◽  
Nitrate Anion ◽  
Absolute Quantum

Herein, we report the magnetic and photoluminescence characterization of coordination polymers (CP) built from the combination of lanthanide(III) ions, pyrimidine-4,6-dicarboxylate (pmdc) ligand and a co-ligand with formula {[Dy(μ-pmdc)(μ-ox)0.5(H2O)3]·2H2O}n (1-Dy), {[Dy(μ3-pmdc)(μ-ox)0.5(H2O)2] ~2.33H2O}n (2-Dy), {[Dy2(μ3-pmdc)(μ4-pmdc)(μ-ox)(H2O)3]·5H2O}n (3-Dy), {[Ln(μ3-pmdc)(μ-ox)0.5(H2O)2]·H2O}n (where Ln(III) = Nd (4-Nd), Sm (4-Sm), Eu (4-Eu) and Dy (4-Dy)) and {[Dy(μ4-pmdc)(NO3)(H2O)]·H2O}n (5-Dy). It must be noted the presence of oxalate anion acting as ditopic co-ligand in compounds 1-Dy, 2-Dy, 3-Dy and 4-Ln, whereas in 5-Dy the nitrate anion plays the role of terminal co-ligand. Direct current measurements carried out for the dysprosium-based CPs reveal almost negligible interactions between Dy3+ ions within the crystal structure, which is confirmed by computed values of the exchange parameters J. In addition, alternating current measurements show field-induced single-molecule magnet (SMM) behavior in compounds 1-Dy, 2-Dy, 4-Dy and 5-Dy, whereas slight-frequency dependence is also observed in 3-Dy. Solid state emission spectra performed at room temperature for those compounds emitting in visible region confirm the occurrence of significant ligand-to-lanthanide charge transfer in view of the strong characteristic emissions for all lanthanide ions. Emission decay curves were also recorded to estimate the emission lifetimes for the reported compounds, in addition to the absolute quantum yields. Among them, the high quantum yield of 25.0% measured for 4-Eu is to be highlighted as a representative example of the good emissive properties of the materials.

scholarly journals Arel – Investigating [Eu(H2O)9]3+ photophysics and creating a method to by-pass luminescence quantum yield determinations

2022 ◽  
Author(s):  
Nicolaj Kofod ◽  
Patrick Nawrocki ◽  
Thomas Just Sørensen
Keyword(s):  
Transition Probabilities ◽  
Lanthanide Ions ◽  
Oscillator Strengths ◽  
Quantum Yields ◽  
Lanthanide Luminescence ◽  
Full Control ◽  
Sample Composition ◽  
Trivalent Lanthanide ◽  
Intensity Changes ◽  
Control Knowledge

Lanthanide luminescence has been treated separate from molecular photophysics, although the underlying phenomena are the same. As the optical transitions observed in the trivalent lanthanide ions are forbidden, they do belong to the group that molecular photophysics have yet to conquer, yet the experimental descriptors remains valid. Determining these have proven challenging as full control/knowledge of sample composition is a prerequisite. This has been achieved, and here the luminescence quantum yields (ϕlum), luminescence lifetimes (τobs), oscillator strengths (f ), and the rates of non-radiative (knr) and radiative (kr ≡ A) deactivation of [Eu(H2O)9]3+ was determined for the trigonal tricapped prismatic (TTP) coordination geometry. Further, it was shown that instead of a full photophysical characterization, it is possible to relate changes in transition probabilities to the relative parameter Arel, which does not require reference data. While Arel does not afford comparisons between experiments, it resolves emission intensity changes due to emitter properties—changes in A—from intensity changes due to environmental effects—changes in knr, and differences in the number of photons absorbed. When working with fluorescence this may seem trivial, when working with lanthanide luminescence it is not.

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