New Heteroligand Europium and Gadolinium Formate Triazole Dicarboxylates: Synthesis, Structures, and Luminescence Properties

Belousov, Yu. A.; Гончаренко, В. Е.; Lunev, A. M.; Sidoruk, A. V.; Bezzubov, Stanislav I.; Тайдаков, И. В.

doi:10.1134/s1070328420050012

Cited by 8 publications

(3 citation statements)

References 30 publications

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“…Apart from the desired reaction, interfering processes could occur, including decomposition of the compounds. Accordingly, in situ generated dimethylammonium cation (CH 3 ) 2 NH 2 + is a frequent guest in many anionic MOF crystal structures due to the solvent (DMF) decomposition in the temperature range of 100–160 °C. − …”

Section: Resultsmentioning

confidence: 99%

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Tuning the Cerium-Based Metal–Organic Framework Formation by Template Effect and Precursor Selection

Grebenyuk,

Shaulskaya,

Shevchenko

et al. 2023

ACS Omega

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The novel metal–organic framework [(CH 3 ) 2 NH 2 ] 2 [Ce 2 (bdc) 4 (DMF) 2 ]·2H 2 O ( Ce-MOF , H 2 bdc—terephthalic acid, DMF— N , N -dimethylformamide) was synthesized by a simple solvothermal method. Ce-MOF has 3D connectivity of bcu type with a dinuclear fragment connected with eight neighbors, while three types of guest species are residing in its pores: water, DMF, and dimethylammonium cations. Dimethylamine was demonstrated to have a decisive templating effect on the formation of Ce-MOF , as its deliberate addition to the solvothermal reaction allows the reproducible synthesis of the new framework. Otherwise, the previously reported MOF Ce 5 (bdc) 7.5 (DMF) 4 ( Ce5 ) or its composite with nano-CeO 2 (CeO 2 @ Ce5 ) was obtained. Various Ce carboxylate precursors and synthetic conditions were explored to evidence the major stability of Ce-MOF and Ce5 within the Ce carboxylate-H 2 bdc-DMF system. The choice of precursor impacts the surface area of Ce-MOF and thus its reactivity in an oxidative atmosphere. The in situ PXRD and TG-DTA-MS study of Ce-MOF in a nonoxidative atmosphere demonstrates that it eliminates H 2 O and DMF along with (CH 3 ) 2 NH guest species in two distinct stages at 70 and 250 °C, respectively, yielding [Ce 2 (bdc) 3 (H 2 bdc)]. The H 2 bdc molecule is removed at 350 °C with the formation of novel modification of Ce 2 (bdc) 3 , which is stable at least up to 450 °C. According to the total X-ray scattering study with pair distribution function analysis, the most pronounced local structure transformation occurs upon departure of DMF and (CH 3 ) 2 NH guest species, which is in line with the in situ PXRD experiment. In an oxidative atmosphere, Ce-MOF undergoes combustion to CeO 2 at a temperature as low as 390 °C. MOF-derived CeO 2 from Ce-MOF , Ce5 , and CeO 2 @ Ce5 exhibits catalytic activity in the CO oxidation reaction.

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Section: Resultsmentioning

confidence: 99%

“…Accordingly, in situ generated dimethylammonium cation (CH 3 ) 2 NH 2 + is a frequent guest in many anionic MOF crystal structures due to the solvent (DMF) decomposition in the temperature range of 100–160 °C. 62 − 70 …”

Section: Resultsmentioning

confidence: 99%

Tuning the Cerium-Based Metal–Organic Framework Formation by Template Effect and Precursor Selection

Grebenyuk,

Shaulskaya,

Shevchenko

et al. 2023

ACS Omega

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“…Triazole and deprotonated phenol-based ligands are known to emit in the 400–500 nm range and can be considered useful components to modulate the emission. Triazole-derived ligands are usually reported in the literature as coordinated to d 10 metal ions. − Among the mentioned lanthanide triazole compounds, those containing Dy III ions exhibit a characteristic yellow emission. − On the other hand, compounds with Eu III ions emit a typical red or orange light, while compounds with Tb III ions emit green light. The combination of Eu III and Tb III with an appropriate ligand may generate white light. , In addition, Dy III coordination polymers emitting white light are less reported in the literature …”

Section: Introductionmentioning

confidence: 99%

Tuning the Emission of Homometallic Dy^III, Tb^III, and Eu^III 1-D Coordination Polymers with 2,6-Di(1H-1,2,4-triazole-1-yl-methyl)-4-R-phenoxo Ligands: Sensitization through the Singlet State

Manzur,

Fuentealba,

Gil

et al. 2023

Inorg. Chem.

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This work reports the structural characterization and photophysical properties of DyIII, TbIII, and EuIII coordination polymers with two phenoxo-triazole-based ligands [2,6-di(1H-1,2,4-triazole-1-yl-methyl)-4-R-phenoxo, LRTr (R = CH3; Cl)]. These ligands permitted us to obtain isostructural polymers, described as a 1D double chain, with LnIII being nona-coordinated. The energies of the ligand triplet (T1) states were estimated using low-temperature time-resolved emission spectra of YIII analogues. Compounds with LClTr present higher emission intensity than those with LMeTr. The emission of TbIII compounds was not affected by the different excitation wavelengths used and was emitted in the pure green region. In contrast, DyL Me Tr emits in the blue-to-white region, while the luminescence of DyL Cl Tr remains in the white region for all excitation wavelengths. On the other hand, EuIII compounds emit in the blue (ligand) or red region (EuIII) depending on the substituent of the phenoxo moiety and excitation wavelength. Theoretical calculations were employed to determine the excited states of the ligands by using time-dependent density functional theory. These calculations aided in modeling the intramolecular energy transfer and rationalizing the optical properties and demonstrated that the sensitization of the LnIII ions is driven via S1 → LnIII, a process that is less common as compared to T1 → LnIII.

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Lanthanide azolecarboxylate compounds: Structure, luminescent properties and applications

Belousov

Дроздов

Taydakov

et al. 2021

Coordination Chemistry Reviews

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New Heteroligand Europium and Gadolinium Formate Triazole Dicarboxylates: Synthesis, Structures, and Luminescence Properties

Cited by 8 publications

References 30 publications

Tuning the Cerium-Based Metal–Organic Framework Formation by Template Effect and Precursor Selection

Tuning the Cerium-Based Metal–Organic Framework Formation by Template Effect and Precursor Selection

Tuning the Emission of Homometallic Dy^III, Tb^III, and Eu^III 1-D Coordination Polymers with 2,6-Di(1H-1,2,4-triazole-1-yl-methyl)-4-R-phenoxo Ligands: Sensitization through the Singlet State

Lanthanide azolecarboxylate compounds: Structure, luminescent properties and applications

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New Heteroligand Europium and Gadolinium Formate Triazole Dicarboxylates: Synthesis, Structures, and Luminescence Properties

Cited by 8 publications

References 30 publications

Tuning the Cerium-Based Metal–Organic Framework Formation by Template Effect and Precursor Selection

Tuning the Cerium-Based Metal–Organic Framework Formation by Template Effect and Precursor Selection

Tuning the Emission of Homometallic DyIII, TbIII, and EuIII 1-D Coordination Polymers with 2,6-Di(1H-1,2,4-triazole-1-yl-methyl)-4-R-phenoxo Ligands: Sensitization through the Singlet State

Lanthanide azolecarboxylate compounds: Structure, luminescent properties and applications

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Tuning the Emission of Homometallic Dy^III, Tb^III, and Eu^III 1-D Coordination Polymers with 2,6-Di(1H-1,2,4-triazole-1-yl-methyl)-4-R-phenoxo Ligands: Sensitization through the Singlet State