Mechanochemical synthesis of an Eu(III) complex. Preparation and Luminescence Properties of PMMA:[C42H38N5O19Eu] Hybrid Films

Rodríguez, S.; Martínez, Pedro César Cantú; Bernès, Syl­vain; Pérez, Netzahualcóyotl Mayek; Bustos, R.; Garcı́a-España, Enrique

doi:10.1016/j.poly.2014.08.041

Cited by 17 publications

(5 citation statements)

References 29 publications

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“…Mechanochemical synthesis has the advantage of reducing the use of solvent and potentially reducing losses of soluble starting materials and products. Mechanochemistry has been used to synthesize various lanthanide complexes including some containing β-diketonates − as well as Ln-based metal–organic frameworks . Mechanochemical reactions can include small amounts of solvent, and the reaction can be described as either “liquid-assisted” or a “slurry” depending on the amount of solvent used relative to the mass of solid reagents. , Reactions where a reagent is a liquid are still considered “neat” reactions and may not be considered “liquid-assisted” .…”

Section: Introductionmentioning

confidence: 99%

Mechanochemical Syntheses of Ln(hfac)₃(H₂O)_x (Ln = La-Sm, Tb): Isolation of 10-, 9-, and 8-Coordinate Ln(hfac)_n Complexes

et al. 2022

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Volatile lanthanide coordination complexes are critical to the generation of new optical and magnetic materials. One of the most common precursors for preparing volatile lanthanide complexes is the hydrate with the general formula Ln(hfac) 3 (H 2 O) x (x = 3 for La-Nd, x = 2 for Sm) (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonato). We have investigated the synthesis of Ln(hfac) 3 (H 2 O) x using more environmentally sustainable mechanochemical approaches. Characterization of the products using Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, elemental analysis, and powder X-ray diffraction shows substantial differences in product distribution between methods. The mechanochemical synthesis of the hydrate complexes leads to a variety of coordination compounds including the expected hydrate product, the known retro-Claisen impurity, and hydrated protonated Hhfac ligand depending on the technique employed. Surprisingly, 10-coordinate complexes of the form Na 2 Ln(hfac) 5 •3H 2 O for Ln = La-Nd were also isolated from reactions using a mortar and pestle. The electrostatic bonding of lanthanide coordination complexes is a challenge for obtaining reproducible reactions and clean products. The reproducibility issues are most acute for the large, early lanthanides whereas for the mid to late lanthanides, reproducibility in terms of product distribution and yield is less of an issue because of their smaller size and greater charge to radius ratio. Ball milling increases reproducibility in terms of generating the desired Ln(hfac) 3 (H 2 O) x along with hydrated Hhfac (tetraol) and free Hhfac products. The results illustrate the dynamic behavior of lanthanide complexes in solution and the solid state as well as the structural diversity available to the early lanthanides.

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Section: Introductionmentioning

confidence: 99%

Mechanochemical Syntheses of Ln(hfac)₃(H₂O)_x (Ln = La-Sm, Tb): Isolation of 10-, 9-, and 8-Coordinate Ln(hfac)_n Complexes

et al. 2022

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“…It has been speculated that the water molecules in an Eu 3+ -based MOF and organic complex could form H-bonds with carbonyl acceptors in the PMMA, or by partial coordination of the carbonyl groups to the metal at the interface. − We expect that such interactions are present between the EuMTA particles and the PHEMA matrix, however, probing these weak interactions in the composite by IR and NMR spectroscopy was uninformative, due to the low weight % loading of the EuMTA in the PHEMA matrix. In addition, several other luminescence quenching sources are decreased as a result of embedding the EuMTA particles in a rigid polymer matrix, such as quenching of the luminescence due to metal–metal interactions, energy loss through nonradiative processes, and surface-located, nonradioactive recombination centers. ,, …”

Section: Resultsmentioning

confidence: 99%

“…In addition, several other luminescence quenching sources are decreased as a result of embedding the EuMTA particles in a rigid polymer matrix, such as quenching of the luminescence due to metal−metal interactions, energy loss through nonradiative processes, and surface-located, nonradioactive recombination centers. 33,43,44 As a result of encapsulating EuMTA in PHEMA, the luminescence lifetime of the EuMTA 616 nm band was significantly increased from 63.8 ± 0.003 μs for the MOF suspension in water to 231.6 ± 0.001 μs (n = 5) for the PHEMA−EuMTA composite. The 616 nm band also showed the steepest increase in the intensity (due to the hypersensitive 5 D 0 → 7 F 2 transition), while the 590 and 690 nm Eu 3+ bands (corresponding to 5 D 0 → 7 F 1 and 5 D 0 → 7 F 4 transitions, respectively) were only moderately impacted by encapsulation of the MOF.…”

Section: Composite Preparation and Optimization Thementioning

confidence: 99%

Europium Metal–Organic Framework Polymer Composites with Enhanced Luminescence and Selective Ferric Ion Sensing

Rozenberga,

Bloch,

Gillam

et al. 2024

ACS Appl. Polym. Mater.

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Ferric ions (Fe 3+ ) play an important role in various biological and chemical processes in living organisms, natural environments, and industry. To understand these roles, a fast and accurate sensor for the selective detection and quantification of Fe 3+ is highly desirable. Herein, we report the development and assessment of a luminescent europium metal−organic framework (MOF, with specific acronym EuMTA, named for the ligand used in the synthesis: 2-methoxyterephthalic acid)�polymer composite material. Immobilizing EuMTA within a cross-linked poly(2hydroxyethyl methacrylate) (PHEMA) matrix resulted in a significant enhancement in the ligand-Eu antenna effect, as well as an increase in the Fe 3+ sensing range (detection of Fe 3+ at concentrations between 2 and 120 ppm) compared to native EuMTA powder (0.16−4 ppm). The PHEMA matrix also functioned to protect the embedded MOF, improving the stability of the sensor under acidic conditions, while enhancing Fe 3+ ion selectivity compared to a EuMTA powder suspension. The MOF-composite sensor exhibited excellent luminescence intensity, stability over prolonged storage (21 days), and reusability. Furthermore, the application of the MOF-composite sensor for mineral processing was successfully demonstrated by monitoring Fe 3+ concentrations using a simulated mineral leaching model.

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“…An effective approach to increase the luminescent efficiency is that chelating Ln ions with organic ligands, which possess advantages such as long emission lifetimes, narrow bandwidths, and large Stokes shifts [23][24][25][26][27][28][29][30][31][32][33][34]. Since the Ln organic complexes are poor in thermal performances, mechanical stabilities, and processing properties, incorporating these complexes into organic polymers is an ideal method to make up these shortcomings [35][36][37][38][39][40][41][42][43]. Poly methyl methacrylate (PMMA) exhibits high transparency in the visible spectral region, excellent weather resistance, and high mechanical strength.…”

Section: Introductionmentioning

confidence: 99%

Photon Conversion and Radiation Synergism in Eu/Tb Complexes Incorporated Poly Methyl Methacrylate

Xiao

Zhang

Wang

et al. 2016

Advances in Materials Science and Engineering

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Green and red emissions in terbium and europium benzoic acids (TBA and EBA) incorporated poly methyl methacrylates (PMMA) are exhibited. Larger intensity parametersΩ2(11.13×10-20 cm2) andΩ4(13.15×10-20 cm2) ofEu3+indicate a high inversion asymmetrical and strong covalent environment around lanthanide (Ln) ions and maximum emission cross sectionσem-max(2.45×10-21 cm2) for the dominant transitionD50→F27ofEu3+reveals the effective photon conversion capacity in EBA incorporated PMMA. Color variation and fluorescence enhancement are validated to be originated from energy transfer and synergistic effect in TBA/EBA coincorporated PMMA system. The results indicate that Eu and Tb complexes incorporated PMMA with effective photon conversion hold great prospect in increment of lighting quality and enhancement of solar-cell efficiency employed in outer space.

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Mechanochemical synthesis of an Eu(III) complex. Preparation and Luminescence Properties of PMMA:[C42H38N5O19Eu] Hybrid Films

Cited by 17 publications

References 29 publications

Mechanochemical Syntheses of Ln(hfac)₃(H₂O)_x (Ln = La-Sm, Tb): Isolation of 10-, 9-, and 8-Coordinate Ln(hfac)_n Complexes

Mechanochemical Syntheses of Ln(hfac)₃(H₂O)_x (Ln = La-Sm, Tb): Isolation of 10-, 9-, and 8-Coordinate Ln(hfac)_n Complexes

Europium Metal–Organic Framework Polymer Composites with Enhanced Luminescence and Selective Ferric Ion Sensing

Photon Conversion and Radiation Synergism in Eu/Tb Complexes Incorporated Poly Methyl Methacrylate

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Mechanochemical synthesis of an Eu(III) complex. Preparation and Luminescence Properties of PMMA:[C42H38N5O19Eu] Hybrid Films

Cited by 17 publications

References 29 publications

Mechanochemical Syntheses of Ln(hfac)3(H2O)x (Ln = La-Sm, Tb): Isolation of 10-, 9-, and 8-Coordinate Ln(hfac)n Complexes

Mechanochemical Syntheses of Ln(hfac)3(H2O)x (Ln = La-Sm, Tb): Isolation of 10-, 9-, and 8-Coordinate Ln(hfac)n Complexes

Europium Metal–Organic Framework Polymer Composites with Enhanced Luminescence and Selective Ferric Ion Sensing

Photon Conversion and Radiation Synergism in Eu/Tb Complexes Incorporated Poly Methyl Methacrylate

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Mechanochemical Syntheses of Ln(hfac)₃(H₂O)_x (Ln = La-Sm, Tb): Isolation of 10-, 9-, and 8-Coordinate Ln(hfac)_n Complexes

Mechanochemical Syntheses of Ln(hfac)₃(H₂O)_x (Ln = La-Sm, Tb): Isolation of 10-, 9-, and 8-Coordinate Ln(hfac)_n Complexes