Modeling the Eu(III)-to-Cr(III) Energy Transfer Rates in Luminescent Bimetallic Complexes
There is a growing interest in alternatives to lanthanide ion (Ln(III))-based luminescence sensitizing chromophores for in vivo applications, mainly in optical biological windows. Transition metals (M) are relevant candidates as chromophores as they have high absorption rates and emission bands cove...
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MDPI AG
2023-01-01
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| Series: | Inorganics |
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| Online Access: | https://www.mdpi.com/2304-6740/11/1/38 |
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| author | Jorge A. A. Coelho Renaldo T. Moura Ricardo L. Longo Oscar L. Malta Albano N. Carneiro Neto |
| author_facet | Jorge A. A. Coelho Renaldo T. Moura Ricardo L. Longo Oscar L. Malta Albano N. Carneiro Neto |
| author_sort | Jorge A. A. Coelho |
| collection | DOAJ |
| description | There is a growing interest in alternatives to lanthanide ion (Ln(III))-based luminescence sensitizing chromophores for in vivo applications, mainly in optical biological windows. Transition metals (M) are relevant candidates as chromophores as they have high absorption rates and emission bands covering a wide range of visible to near-infrared spectrum. However, despite the importance of theoretical models for the design of M–Ln(III) complexes, few contributions have devoted efforts to elucidating the energy transfer (ET) processes between M and Ln(III) ions. In this context, we adapted the intramolecular energy transfer (IET) to calculate, for the first time, the energy transfer rates for M–Ln(III) complexes. A new model was proposed that considers the assistance of phonons in the calculation of ET rates. As an example, the proposed model can estimate the ET rates between Eu(III) and Cr(III) ions in the [CrEuL<sub>3</sub>]<sup>6+</sup> complex (where L = 2-{6-[N,N-diethylcarboxamido]pyridin-2-yl}-1,1′-dimethyl-5,5′-methylene-2′-(5-methylpyridin-2-yl)bis [1H-benzimidazole]). The calculated rates (930–1200 s<sup>−1</sup>) are in excellent agreement with the experimentally available data (750–1200 s<sup>−1</sup>) when a phonon-assisted energy transfer process is considered. Thus, this proposed model can be useful to predict and explain photophysical properties driven by the energy transfer between Ln(III) ions and transition metals. |
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| language | English |
| last_indexed | 2024-03-09T12:15:22Z |
| publishDate | 2023-01-01 |
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| record_format | Article |
| series | Inorganics |
| spelling | doaj.art-ec20ebf3455646fbba3e70c1d18a6c652023-11-30T22:47:26ZengMDPI AGInorganics2304-67402023-01-011113810.3390/inorganics11010038Modeling the Eu(III)-to-Cr(III) Energy Transfer Rates in Luminescent Bimetallic ComplexesJorge A. A. Coelho0Renaldo T. Moura1Ricardo L. Longo2Oscar L. Malta3Albano N. Carneiro Neto4Department of Fundamental Chemistry, Federal University of Pernambuco, Recife 50740-560, BrazilDepartment of Chemistry, Southern Methodist University, Dallas, TX 75275-0314, USADepartment of Fundamental Chemistry, Federal University of Pernambuco, Recife 50740-560, BrazilDepartment of Fundamental Chemistry, Federal University of Pernambuco, Recife 50740-560, BrazilPhysics Department and CICECO—Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, PortugalThere is a growing interest in alternatives to lanthanide ion (Ln(III))-based luminescence sensitizing chromophores for in vivo applications, mainly in optical biological windows. Transition metals (M) are relevant candidates as chromophores as they have high absorption rates and emission bands covering a wide range of visible to near-infrared spectrum. However, despite the importance of theoretical models for the design of M–Ln(III) complexes, few contributions have devoted efforts to elucidating the energy transfer (ET) processes between M and Ln(III) ions. In this context, we adapted the intramolecular energy transfer (IET) to calculate, for the first time, the energy transfer rates for M–Ln(III) complexes. A new model was proposed that considers the assistance of phonons in the calculation of ET rates. As an example, the proposed model can estimate the ET rates between Eu(III) and Cr(III) ions in the [CrEuL<sub>3</sub>]<sup>6+</sup> complex (where L = 2-{6-[N,N-diethylcarboxamido]pyridin-2-yl}-1,1′-dimethyl-5,5′-methylene-2′-(5-methylpyridin-2-yl)bis [1H-benzimidazole]). The calculated rates (930–1200 s<sup>−1</sup>) are in excellent agreement with the experimentally available data (750–1200 s<sup>−1</sup>) when a phonon-assisted energy transfer process is considered. Thus, this proposed model can be useful to predict and explain photophysical properties driven by the energy transfer between Ln(III) ions and transition metals.https://www.mdpi.com/2304-6740/11/1/38energy transferlanthanidetransition metalphonon-assisted processtheoretical calculationsheterometallic complexes |
| spellingShingle | Jorge A. A. Coelho Renaldo T. Moura Ricardo L. Longo Oscar L. Malta Albano N. Carneiro Neto Modeling the Eu(III)-to-Cr(III) Energy Transfer Rates in Luminescent Bimetallic Complexes Inorganics energy transfer lanthanide transition metal phonon-assisted process theoretical calculations heterometallic complexes |
| title | Modeling the Eu(III)-to-Cr(III) Energy Transfer Rates in Luminescent Bimetallic Complexes |
| title_full | Modeling the Eu(III)-to-Cr(III) Energy Transfer Rates in Luminescent Bimetallic Complexes |
| title_fullStr | Modeling the Eu(III)-to-Cr(III) Energy Transfer Rates in Luminescent Bimetallic Complexes |
| title_full_unstemmed | Modeling the Eu(III)-to-Cr(III) Energy Transfer Rates in Luminescent Bimetallic Complexes |
| title_short | Modeling the Eu(III)-to-Cr(III) Energy Transfer Rates in Luminescent Bimetallic Complexes |
| title_sort | modeling the eu iii to cr iii energy transfer rates in luminescent bimetallic complexes |
| topic | energy transfer lanthanide transition metal phonon-assisted process theoretical calculations heterometallic complexes |
| url | https://www.mdpi.com/2304-6740/11/1/38 |
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