A Europium(III) Complex with an Unusual Anion–Cation Interaction: A Luminescent Molecular Thermometer for Ratiometric Temperature Sensing

Outis, Mani; Laia, César A. T.; Oliveira, M. Conceição; Monteiro, Bernardo; Pereira, Cláudia C. L.

doi:10.1002/cplu.202000034

Cited by 17 publications

(20 citation statements)

References 36 publications

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“…In this study we reported for a room temperature ionic liquid, a progressive colour evolution from light yellow to purple close to 80 °C, ascribed to partial β‐diketonate ligand decoordination, with simultaneous formation of a strong interaction between the cation and the negatively charged monocoordinated β‐diketonate moiety [24] . In this work it is also referred that the cationic moiety of [Eu(β‐diketonate) 4 ] − salts has a strong influence on the geometry of the anion and consequently on the emissive properties of the Eu(III) complex [25–26] . Based on this feature, we present a temperature responsive Eu‐based salt that uses the ratio I( 5 D 0 → 7 F 2 )/I( 5 D 0 → 7 F 1 ), linearly related with temperature.…”

Section: Introductionmentioning

confidence: 60%

“…Pioneering work by Yuasa and Kawai, uses the concept that the emissive Eu(III) centre undergoes a significant increment in emission intensity at 616 nm (shoulder), relative to the emission at 613 nm, directly related with the temperature of exposure [36] . Recently we have studied the use of the [Chol][Eu(fod) 4 ] (Chol=Cholinium) as a luminescent molecular thermometer for ratiometric temperature sensing up to 95 °C based on the ratio between the emission intensity of the shoulder at 616 nm and the maximum intensity of the 5 D 0 → 7 F 2 transition at 613 nm [26] . This feature is also characteristic of 1 although the desired linearity in temperature responsive systems was found using a different ratio as will be discussed further.…”

Section: Resultsmentioning

confidence: 99%

“…7 F 2 transition at 613 nm. [26] This feature is also characteristic of 1 although the desired linearity in temperature responsive systems was found using a different ratio as will be discussed further.…”

Section: Thermochromic and Photophysical Studiesmentioning

confidence: 90%

“…[24] In this work it is also referred that the cationic moiety of [Eu(β-diketonate) 4 ] À salts has a strong influence on the geometry of the anion and consequently on the emissive properties of the Eu(III) complex. [25][26] Based on this feature, we present a temperature responsive Eu-based salt that uses the ratio I( 5 D 0 ! 7 F 2 )/I( 5 D 0 !…”

Section: Introductionmentioning

confidence: 99%

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A Europium(III) Complex Embedded in a Polysulfone Host Matrix: A Flexible Film with Temperature‐Responsive Ratiometric Behaviour

et al. 2020

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An emissive europium(III) complex [C 2 mim][Eu(fod) 4 ] (1; C 2 mim = 1-ethyl-3-methyl-imidazolium; fod = 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyloctane-4,6-dionate) was prepared. The complex shows ratiometric thermal behaviour up to 155°C. These unusual temperature-dependent properties arise from a solidsolid phase transition that promotes increased contact between the anion and the cation, affecting the emission profile of the emissive anion in two different ratiometric relations. A ultra-bright and flexible emissive photopolymer film was obtained using polysulfone (PSU) as the host matrix of 10 % (w/w) of 1, that also induced changes on the lanthanide emissive profile with temperature. A temperature-responsive luminescent film 1/PSU is sensitivr to heating between 100 and 155°C. Also, the emission lifetime of 1 was not affected by confinement in PSU, while its emission quantum yield was reduced from 82 to 59 %.

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Section: Introductionmentioning

confidence: 60%

Section: Resultsmentioning

confidence: 99%

Section: Thermochromic and Photophysical Studiesmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

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A Europium(III) Complex Embedded in a Polysulfone Host Matrix: A Flexible Film with Temperature‐Responsive Ratiometric Behaviour

et al. 2020

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“…Редкоземельные ионы в свою очередь обладают рядом преимуществ, таких как химическая инертность, устойчивость к радиационным центрам окраски, долговременная стабильность флуоресценции. Существует большое количество исследований, посвященных изучению оптической чувствительности ионов Eu, Dy, Ho, Er и Tm в различных стеклах [9][10][11][12][13]. Например, Er 3+ имеет два близко расположенных уровня энергии, соответствующие термически связанным переходам 2 H 11/2 , 4 S 3/2 → 4 I 15/2 в зеленой области спектра (около 520 nm и 550 nm) с небольшим энергетическим зазором (800 cm −1 ).…”

Section: Introductionunclassified

Калибровка Температуры По Нормированным Спектрам Ап-Конверсионной Флуоресценции Германатных Стекол И Стеклокерамик, Активированных Ионами Эрбия И Иттербия

Асеев¹,

Борисевич²,

Ходасевич³

et al. 2021

Оптика И Спектроскопия

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To select erbium and ytterbium doped germanate glasses and glass ceramics, which are most suitable as sensitive elements of fluorescent temperature sensors, a multivariate model of temperature calibration has been developed based on principal component analysis, cluster analysis and interval projection to latent structures of up-conversion green fluorescence spectra. The calibration model used 95 spectral variables for the GeO2-Na2O-Yb2O3-MgO-La2O3-Er2O3 glass-ceramic is characterized by the best quality parameters: the root-mean-square error is 0.37 K, the residual prediction deviation for the test subset is greater than 102, and the relative error does not exceed 0.20%.

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Novel and High‐Sensitive Primary and Self‐Referencing Thermometers Based on the Excitation Spectra of Lanthanide Ions

Souza

Silva

et al. 2022

Advanced Optical Materials

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At the micro-and nanoscale, thermometry has been regarded as fundamental to develop underlying laws of heat transfer, [8][9][10][11] to design and improve new circuits, [12,13] to comprehend quantitatively heat exchange within cells and tissues, [14][15][16] and to harmlessly apply hyperthermia therapy. [17][18][19] In this context, ratiometric approaches for molecular (or nano) thermometry are widely employed because of their precision, easiness, and high relative thermal sensitivity (S r ). [3,[20][21][22][23] Usually, a ratio of emission (integrated) intensities is used as the thermometric parameter (Δ) due to the high sensitivity of emission-based techniques allowing, for instance, singleparticle spectroscopy. [24] Indeed, photoluminescence of lanthanide trivalent ions (Ln(III)) is especially suitable for these measurements [3,25,26] due to their unique features such as high emission intensities, narrow excitation, and emission bands, long emission lifetimes (µs to ms), and spectral ranges from UV-vis to nearinfrared (NIR). [27,28] In addition, the energies of the intra-4f transitions are nearly independent of their surroundings, e.g., ligands, host crystal, solvent, etc. [29] This allows for prompt assignments of excitation and emission spectra and predictable energy differences. [27][28][29] These features have contributed to the accelerated development of Ln(III)-based thermometers in recent years, [3,25] including Remote sensing through ratiometric luminescence thermometry based on trivalent lanthanide ions (Ln(III)) has lately become a promising technique due to its numerous applications. Most available Ln(III)-based luminescentthermometers require a calibration process with a reference thermal probe (secondary thermometers) and recurrent calibrations are mandatory, particularly when the thermometers are used in different media. This is sometimes impractical and a medium-independent calibration relation is postulated, which is potentially inaccurate. Thus, the determination of the temperature based on well-grounded physical principles by primary thermometers is the only way to overcome these challenges. Despite being considered one of the most important developments in luminescence thermometry, primary luminescent thermometers are scarce. Primary thermometers requiring calibration are proposed, implemented, and validated at one known temperature (primary-T), which are also self-referencing, employing ratiometric data from the excitation spectrum of Ln(III). By combining with the emission spectrum, thermometers not requiring calibration (primary-S) are devised. An Eu(III)-β-diketonate complex is used as a proof-of-concept, but the approach is universal and other Ln(III)-based materials can be explored. Because many thermometric parameters are employed for temperature prediction an unprecedented very high accuracy of 0.2% in the physiological range is obtained.

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A Europium(III) Complex with an Unusual Anion–Cation Interaction: A Luminescent Molecular Thermometer for Ratiometric Temperature Sensing

Cited by 17 publications

References 36 publications

A Europium(III) Complex Embedded in a Polysulfone Host Matrix: A Flexible Film with Temperature‐Responsive Ratiometric Behaviour

A Europium(III) Complex Embedded in a Polysulfone Host Matrix: A Flexible Film with Temperature‐Responsive Ratiometric Behaviour

Калибровка Температуры По Нормированным Спектрам Ап-Конверсионной Флуоресценции Германатных Стекол И Стеклокерамик, Активированных Ионами Эрбия И Иттербия

Novel and High‐Sensitive Primary and Self‐Referencing Thermometers Based on the Excitation Spectra of Lanthanide Ions

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