Modeling intramolecular energy transfer in lanthanide chelates: A critical review and recent advances

Neto, Albano N. Carneiro; Teotonio, Ercules E.S.; de, Gilberto F.; Brito, Hermi F.; Legendziewicz, J.; Carlos, Luı́s D.; Felinto, Maria C.F.C.; Gawryszewska, Paula; Moura, Renaldo T.; Longo, Ricardo L.; Faustino, Wagner M.; Malta, O.L.

doi:10.1016/bs.hpcre.2019.08.001

Cited by 77 publications

(74 citation statements)

References 296 publications

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“…The europium ion is well known as a perfect probe for chemical surroundings, owing to its electronic configuration [ 16 , 17 , 18 ]. The luminescence spectra of the Eu complexes studied demonstrate the characteristic transitions of the Eu 3+ ion from the excited state 5 D 0 to the ground state 7 F J ( J = 0–4) as well as from the 5 D 1 state in the complex 9 ( Figure 5 ).…”

Section: Resultsmentioning

confidence: 99%

“…As a result of such charge redistribution, ILCT state appears and participates in the sensitization of Ln 3+ ion luminescence. It should be noted also that in the case of Eu complexes, owing to the low redox potential of this ion, the ligand to metal charge transfer (LMCT) state may have low energy and cause the luminescence quenching [ 17 , 18 ]. Therefore, the energies of S 1 and T states are very important for the optimization of intraligand energy transfer, but charge transfer states can also have a dramatic influence on the efficiency of this transfer.…”

Section: Resultsmentioning

confidence: 99%

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Diarylphosphate as a New Route for Design of Highly Luminescent Ln Complexes

et al. 2020

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Organophosphate-chloride complexes [{(2,6-iPr2C6H3-O)2POO}2LnCl(CH3OH)4]·2CH3OH, Ln = Nd (1), Eu (2), Gd (3), and Tb (4) have been obtained and structurally characterized. Their reaction with 2,2′:6′,2″-terpyridine leads to the formation of 1:1 adducts ([{(2,6-iPr2C6H3-O)2POO}2LnCl(terpy)(H2O)2(CH3OH)], Ln = Eu (5), Gd (6), Tb (7) with exception of Nd, where tris-diisopropylphenylphosphate complex [{(2,6-iPr2C6H3-O)2POO}3Nd) (terpy)(H2O)(CH3OH)] (8) was obtained due to the ligand metathesis. A bright luminescence observed for the Eu and Tb organophosphate complexes is the first example of an application of organophosphate ligands for 4f-ions luminescence sensitization. Photophysical properties of all complexes were analyzed by optical spectroscopy and an energy transfer scheme was discussed. A combination of two types of ligands into the coordination sphere (phosphate and phenanthroline) allows designing the Eu surrounding with very high intrinsic quantum yield QEuEu (0.92) and highly luminescent Ln complexes for both visible and near-infrared (NIR) regions.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Diarylphosphate as a New Route for Design of Highly Luminescent Ln Complexes

et al. 2020

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“…To rationalize these thermal dependences, we use time-dependent density functional theory and intramolecular energy transfer calculations (details in Supporting Information). The intramolecular energy transfer rates for Ln 3+ complexes were estimated based on a well-defined theory. − …”

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confidence: 99%

Real-Time Intracellular Temperature Imaging Using Lanthanide-Bearing Polymeric Micelles

et al. 2020

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Measurement of thermogenesis in individual cells is a remarkable challenge due to the complexity of the biochemical environment (such as pH and ionic strength) and to the rapid and yet not well-understood heat transfer mechanisms throughout the cell. Here, we present a unique system for intracellular temperature mapping in a fluorescence microscope (uncertainty of 0.2 K) using rationally designed luminescent Ln 3+ -bearing polymeric micellar probes (Ln=Sm, Eu) incubated in breast cancer MDA-MB468 cells.2D thermal images recorded increasing the temperature of the cells culture medium between 296 and 304 K shows inhomogeneous intracellular temperature progressions up to ~20 degrees and subcellular gradients of ~5 degrees between the nucleolus and the rest of the cell, illustrating the thermogenic activity of the different organelles and highlighting the potential of this tool to study intracellular processes.

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“…In lanthanide spectroscopy, the electric dipole transitions between 2 S +1 L J and 2 S ′+1 L J ′ ′ states (| SLJ ⟩ → | S ′ L ′ J ′⟩) have to obey the selection rule on the J quantum number, | J – J ′| ≤ λ ≤ J + J ′ (with λ = 2, 4, and 6), for nonzero S ′ L ′ J ′ U (λ) SLJ matrix elements. , In this sense, the Eu 3+ ion has unique properties, especially regarding its emission spectrum where it is possible to directly obtain the Judd–Ofelt intensity parameters Ω λ (λ = 2, 4, and 6) in terms of the integrated areas under the emission curves . This is feasible due to the employment of the 5 D 0 → 7 F 1 emission as an internal reference.…”

Section: Conclusion On the Performances Of The Dlwgsmentioning

confidence: 99%

“…The radiative rate A 0→1 contribution of the 5 D 0 → 7 F 1 transition (in units of s –1 ) can be calculated as , where n is the refractive index which depends upon the wavelength λ and ν̃ is the wavenumber corresponding to the barycenter of the 5 D 0 → 7 F 1 transition.…”

Section: Conclusion On the Performances Of The Dlwgsmentioning

confidence: 99%

Dielectric-Loaded Waveguides as Advanced Platforms for Diagnostics and Application of Transparent Thin Films

et al. 2021

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An alternative approach to classical surface plasmon resonance spectroscopy is dielectric-loaded waveguide (DLWG) spectroscopy, widely used in the past decades to investigate bio-interaction kinetics. Despite their wide application, a successful and clear approach to use the DLWGs for the one-step simultaneous determination of both the thickness and refractive index of organic thin films is absent in the literature. We propose here, for the first time, an experimental protocol based on the multimodal nature of DLWGs to be followed in order to evaluate the optical constants and thickness of transparent thin films with a unique measurement. The proposed method is general and can be applied to every class of transparent organic materials, with a resolution and accuracy which depend on the nature of the external medium (gaseous or liquid), the geometrical characteristics of the DLWG, and the values of both the thickness and dielectric constant of the thin film. From the experimental point of view, the method is demonstrated in a nitrogen environment with an accuracy of about 3%, for the special case of electroluminescent thin films of Eu3+β-diketonate complexes, with an average thickness of about 20 nm. The high value of the refractive index measured for the thin film with the Eu(btfa)3(t-bpete) complex was confirmed by the use of a spectroscopic model based on the Judd–Ofelt theory, in which the magnetic dipole transition 5D0 → 7F1 (Eu3+) for similar films containing Eu3+ complexes is taken as a reference. The DLWGs are finally applied to control the refractive index changes of the organic thin films under UVA irradiation, with potential applications in dosimetry and monitoring light-induced transformation in organic thin films.

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Modeling intramolecular energy transfer in lanthanide chelates: A critical review and recent advances

Cited by 77 publications

References 296 publications

Diarylphosphate as a New Route for Design of Highly Luminescent Ln Complexes

Diarylphosphate as a New Route for Design of Highly Luminescent Ln Complexes

Real-Time Intracellular Temperature Imaging Using Lanthanide-Bearing Polymeric Micelles

Dielectric-Loaded Waveguides as Advanced Platforms for Diagnostics and Application of Transparent Thin Films

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