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On the Experimental Determination of 4f–4f Intensity Parameters from the Emission Spectra of Europium (III) Compounds

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Abstract

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 \({\text{Q}}_{{{\text{Ln}}}}^{{{\text{Ln}}}}\). 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.

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ACKNOWLEDGMENTS

The authors thank the Brazilian funding agencies: Conselho Nacional do Desenvolvimento Científico e Tecnológico (CNPq), Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES), and Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP). L. Blois is grateful to FAPESP for the Ph.D. scholarship (Grant 2020/16795-6). A.N. Carneiro Neto is thankful to SusPhotoSolutions—Soluções Fotovoltaicas Sustentáveis, CENTRO-01-0145-FEDER-000005. R.L. Longo is grateful for the partial financial support under grants: Pronex APQ-0675-1.06/14, INCT-NANOMARCS APQ-0549-1.06/17, APQ-1007-1.06/15, and CNPq-PQ fellowship (Grant 309177/2018-9). I.F. Costa is grateful to CNPq for his post doctorate scholarship (Grant 151623/2020-1). H.F. Brito is grateful to CNPq for the research grant (306951/2018-5). L. Blois also thanks Prof. Erick Bastos and Frank Quina (Instituto de Química—USP) for making the Edinburgh FLS980 Fluorometer available. The authors are thankful to the Analytical Central of the Institute of Chemistry (Central Analítica—IQUSP) for the elemental and mass spectrometry analyses. This paper is dedicated to Professor Marina Popova.

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Authors and Affiliations

  1. Department of Fundamental Chemistry, Institute of Chemistry, University of São Paulo, São Paulo, Brazil

    Lucca Blois, Israel F. Costa, Tiago B. Paolini & Hermi F. Brito

  2. Physics Department and CICECO—Aveiro Institute of Materials, University of Aveiro, Aveiro, Portugal

    Albano N. Carneiro Neto

  3. Department of Fundamental Chemistry, Federal University of Pernambuco, Recife, Brazil

    Ricardo L. Longo & Oscar L. Malta

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  1. Lucca Blois
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  2. Albano N. Carneiro Neto
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  4. Israel F. Costa
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  5. Tiago B. Paolini
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Contributions

L. Blois: Conceptualization, Methodology, Investigation, Formal Analysis, Visualization, Data Curation, Writing—original draft, Writing—review and editing. A.N. Carneiro Neto: Conceptualization, Methodology, Formal Analysis, Validation Writing—original draft, Writing— review and editing. R.L. Longo: Formal Analysis, Validation, Writing—original draft, Writing—review and editing. I.F. Costa: Methodology, Visualization, Data Curation, Writing—original draft, Writing—review and editing. T.B. Paolini: Methodology, Writing—review and editing. H.F. Brito: Conceptualization, Methodology, Visualization, Data Curation, Supervision, Funding Acquisition, Project Administration, Writing—original draft, Writing—review and editing. O.L. Malta: Conceptualization, Methodology, Formal Analysis, Visualization, Supervision, Writing—original draft, Writing—review and editing.

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Correspondence to Hermi F. Brito or Oscar L. Malta.

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Blois, L., Neto, A.N., Longo, R.L. et al. On the Experimental Determination of 4f–4f Intensity Parameters from the Emission Spectra of Europium (III) Compounds. Opt. Spectrosc. 130, 10–17 (2022). https://doi.org/10.1134/S0030400X2201009X

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