Search Results (11)

Lanthanide coordination polymers have been developed at a fast rate during the past two decades due to their appealing applications in the modern field of materials science and emerging technologies like luminescence, magnetism, sensing, gas adsorption, and catalysis. The role of lanthanides in imparting specific properties to the coordination polymers has been fully documented in extensive studies carried out by numerous research groups. It has been shown that because lanthanide(III) ions possess a variable coordination number, they readily build two-dimensional and three-dimensional architectures with definite channels, permanent pores, and distinct surface areas. Due to their strong oxophilic propensity and hard Lewis acid character, lanthanides favor the construction of stable coordination polymers and MOF configurations by strongly binding the coordinating groups of the organic linkers. Associated with palladium complexes, the lanthanide ions provide synergistic effects with Lewis acid sites, beneficial to the catalytic activity. These attractive characteristics of lanthanides enabled them to be fruitfully applied in Pd-Ln coordination polymers with catalytic properties. This review covers an array of Pd-Ln coordination polymers applied as heterogeneous catalysts in Suzuki–Miyaura C(sp²)-C(sp²) cross-coupling reactions. The activity and chemoselectivity of Pd(II) ions and Pd nanoparticles associated in coordination polymers with different lanthanides from a selected array of rare earth elements (Eu, Sm, Eu, Gd, Pr, Nd, Ce, La, or Tb) is discussed. High yields (>99%) are attained under optimized reaction conditions. The specific role of lanthanides and organic ligands in creating sustainable and recyclable heterogeneous Pd catalysts is evidenced. Mechanistic aspects of the C(sp²)-C(sp²) cross-coupling reactions are considered. The synergistic interaction between lanthanides and palladium as well as with the organic ligands is highlighted. Full article

Tuning a material’s hydrophobicity is desirable in several industrial applications, such as hydrocarbon storage, separation, selective CO₂ capture, oil spill cleanup, and water purification. The introduction of fluorine into rare-earth (RE) metal–organic frameworks (MOFs) can make them hydrophobic. In this work, the linker bis(trifluoromethyl)terephthalic acid (TTA) was used to make highly fluorinated MOFs. The reaction of the TTA and RE³⁺ (RE: Y, Gd, or Eu) ions resulted in the primitive cubic structure (pcu) exhibiting RE dimer nodes (RE-TTA-pcu). The crystal structure of the RE-TTA-pcu was obtained. The use of the 2-fluorobenzoic acid in the synthesis resulted in fluorinated hexaclusters in the face-centered cubic (fcu) framework (RE-TTA-fcu), analogous to the UiO-66 MOF. The RE-TTA-fcu has fluorine on the linker as well as in the cluster. The MOFs were characterized by powder X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis, and contact angle measurements. Full article

New heterometallic antenna terephthalate MOFs, namely, (Eu_xM_1−x)₂bdc₃·4H₂O (M = Y, La, Gd) (x = 0.001–1), were synthesized by a one-step method from aqueous solutions. The resulting compounds are isomorphic to each other; the crystalline phase corresponds to Ln₂bdc₃∙4H₂O. Upon 300 nm excitation to the singlet excited state of terephthalate ions, all compounds exhibit a bright red emission corresponding to the of ⁵D₀–⁷F_J (J = 0–4) f-f transitions of Eu³⁺ ions. The Eu(III) concentration dependence of the photophysical properties was carefully studied. We revealed that Gd-doping results in photoluminescence enhancement due to the heavy atom effect. To quantitatively compare the antenna effect among different compounds, we proposed the new approach, where the quantum yield of the ⁵D₀ formation is used to characterize the efficiency of energy transfer from the ligand antenna to the Eu³⁺ emitter. Full article

In this work, three series of micro-sized heterometallic europium-containing terephthalate MOFs, (Eu_1-xLn_x)₂bdc₃·nH₂O (Ln = La, Gd, Lu), are synthesized via an ultrasound-assisted method in an aqueous medium. La³⁺ and Gd³⁺-doped terephthalates are isostructural to Eu₂bdc₃·4H₂O. Lu³⁺-doped compounds are isostructural to Eu₂bdc₃·4H₂O with Lu contents lower than 95 at.%. The compounds that are isostructural to Lu₂bdc₃·2.5H₂O are formed at higher Lu³⁺ concentrations for the (Eu_1-xLu_x)₂bdc₃·nH₂O series. All materials consist of micrometer-sized particles. The particle shape is determined by the crystalline phase. All the synthesized samples demonstrate an “antenna” effect: a bright-red emission corresponding to the ⁵D₀-⁷F_J transitions of Eu³⁺ ions is observed upon 310 nm excitation into the singlet electronic excited state of terephthalate ions. The fine structure of the emission spectra is determined by the crystalline phase due to the different local symmetries of the Eu³⁺ ions in the different kinds of crystalline structures. The photoluminescence quantum yield and ⁵D₀ excited state lifetime of Eu³⁺ are equal to 11 ± 2% and 0.44 ± 0.01 ms, respectively, for the Ln₂bdc₃·4H₂O structures. For the (Eu_1-xLu_x)₂bdc₃·2.5H₂O compounds, significant increases in the photoluminescence quantum yield and ⁵D₀ excited state lifetime of Eu³⁺ are observed, reaching 23% and 1.62 ms, respectively. Full article

Lanthanide Metal–Organic Frameworks (LnMOFs), in recent years, have developed into an interesting subclass of MOFs. While the number of published papers, in particular, were dedicated to their synthesis and functional properties, along with the application mechanisms of MOFs, only a few of them have been focused on LnMOFs thin films independently. LnMOFs have become interesting thanks to their outstanding properties, for example, excellent structural flexibility, tunable pore size, surface area, functionality, and good chemical stability. Significant progress over the past two decades in the preparation of MOF films has been achieved, especially towards the development of green, or at least greener, synthesis approaches. We begin with insight into various types of MOFs and summarize recent achievements in the production of LnMOF films, along with various film preparation approaches. Afterward, we briefly discuss the applications of luminescence features of lanthanide ions in films and their potential as white-light source materials. We also covered films based on Eu, Tb, and Gd with particular accents on different design approaches. Moreover, specifically, luminescent features applied for sensing temperature, a variety of ions, gases, and biomolecules are highlighted. The review ends with a comprehensive conclusion about the state-of-art-potential of LnMOFs together with an outlook on the future of LnMOF films in future technologies. Full article

The present work reports on a detailed discussion about the synthesis, characterization, and luminescence properties of three pairs of enantiopure 3D metal–organic frameworks (MOFs) with general formula {[Ln₂(L/D-tart)₃(H₂O)₂]·3H₂O}_n (3D_Ln-L/D, where Ln = Sm(III), Eu(III) or Gd(III), and L/D-tart = L- or D-tartrate), and ten pairs of enantiopure 2D coordination polymers (CPs) with general formula [Ln(L/D-Htart)₂(OH)(H₂O)₂]_n (2D_Ln-L/D, where Ln = Y(III), Sm(III), Eu(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III) or Yb(III), and L/D-Htart = hydrogen L- or D-tartrate) based on single-crystal X-ray structures. Enantiopure nature of the samples has been further corroborated by Root Mean Square Deviation (RMSD) as well as by circular dichroism (CD) spectra. Solid-state emission spectra of Eu(III), Tb(III), and Dy(III)-based compounds confirm the occurrence of ligand-to-metal charge transfers in view of the characteristic emissions for these lanthanide ions, and emission decay curves were also recorded to estimate the emission lifetimes for the reported compounds. A complete theoretical study was accomplished to better understand the energy transfers occurring in the Eu-based counterparts, which allows for explaining the different performances of 3D-MOFs and 2D-layered compounds. As inferred from the colorimetric diagrams, emission characteristics of Eu-based 2D CPs depend on the temperature, so their luminescent thermometry has been determined on the basis of a ratiometric analysis between the ligand-centered and Eu-centered emission. Finally, a detailed study of the polarized luminescence intensity emitted by the samples is also accomplished to support the occurrence of chiro-optical activity. Full article

Four new isostructural 3d-4f mixed metal organic frameworks (MOFs) Cu Gd₂ (BDC)₄, compound 1, Cu Ho₂ (BDC)₄, compound 2, Cu Eu₂ (BDC)₄, compound 3, and Cu Dy₂ (BDC)₄, compound 4 were successfully synthesized. The structure, stability, and magnetic properties were analyzed. Each MOF has two lanthanide ions and one copper ion node with terephthalic acid as the organic linker. The lanthanide ions form a dimer with each having a capped trigonal prismatic geometry while the copper ion has a square planar geometry. Each of these MOFs shows varying degrees of antiferromagnetic interactions. Full article

This study presents the synthesis, structural and luminescence properties for lanthanide metal–organic frameworks (LnMOFs), which belong to the sub-class of coordination polymers. The series of nanosized LnMOFs (Ln = Eu, Gd, Tb, Eu_0.5Gd_0.5, Tb_0.5Gd_0.5 and Eu_0.5Tb_0.5) was prepared by solvothermal synthesis using a modulator (sodium acetate). We investigated the various surface chemistry compositions of the isostructural LnMOFs with a [Ln(btc)] structure (BTC: Benzene-1,3,5-tricarboxylate) by X-ray photoelectron spectroscopy (XPS). The XPS confirmed the mixed-valent Eu³⁺ and Eu²⁺ compounds, and the presence of Tb in both +3 and +4 valence states, and one +3 valency of Gd. A nanostructure of mixed LnMOFs (EuGd, TbGd and EuTb) with a rod-like shape is related to luminescence properties. The MOFs (EuTb and EuGd) presented Comission Internationale de l’Éclairage (CIE) chromaticities of x = 0.666 and y = 0.331, and x = 0.654 and y = 0.348, respectively, in the red region. They were better than the values desired for use in commercial phosphors, which are x = 0.64 and y = 0.35. For [Tb/Gd(btc)], the CIE coordinates were x = 0.334 and y = 0.562, presenting emissions in the green region. Bimetallic LnMOFs are very promising UV light sensors for biological applications. Full article

Four lanthanide metal-organic frameworks (Ln-MOFs), namely {[Me₂NH₂][LnL]·2H₂O}_n (Ln = Eu 1, Tb 2, Dy 3, Gd 4), have been constructed from a new tetradentate ligand 1-(3,5-dicarboxylatobenzyl)-3,5-pyrazole dicarboxylic acid (H₄L). These isostructural Ln-MOFs, crystallizing in the monoclinic P2₁/c space group, feature a 3D structure with 7.5 Å × 9.8 Å channels along the b axis and the point symbol of {4¹⁰.6¹⁴.8⁴} {4⁵.6}₂. The framework shows high air and hydrolytic stability, which can keep stable after exposed to humid air for 30 days or immersed in water for seven days. Four MOFs with different lanthanide ions (Eu³⁺, Tb³⁺, Dy³⁺, and Gd³⁺) ions exhibit red, green, yellow, and blue emissions, respectively. The Tb-MOF emitting bright green luminescence can selectively and rapidly (<40 s) detect Fe³⁺ in aqueous media via a fluorescence quenching effect. The detection shows excellent anti-inference ability toward many other cations and can be easily recognized by naked eyes. In addition, it can also be utilized as a rapid fluorescent sensor to detect acetone solvent as well as acetone vapor. Similar results of sensing experiments were observed from Eu-MOF. The sensing mechanism are further discussed. Full article

Gadolinium metal-organic frameworks (Gd-MOFs) and Eu-doped Gd-MOFs have been synthesized through a one-pot green approach using commercially available reagents. The 1,4-benzenedicarboxylic acid (H₂-BDC) and 2,6-naphthalenedicarboxylic acid (H₂-NDC) were chosen as ditopic organic linkers to build the 3D structure of the network. The Gd-MOFs were characterized using powder X-ray diffraction (XRD), FT-IR spectroscopy, field emission scanning electron microscopy (FE-SEM) and N₂ adsorption–desorption analysis. The Gd-MOF structures were attributed comparing the XRD patterns, supported by the FT-IR spectra, with data reported in the literature for Ln-MOFs of similar lanthanide ionic radius. FE-SEM characterization points to the effect of the duration of the synthesis to a more crystalline and organized structure, with grain dimensions increasing upon increasing reaction time. The total surface area of the MOFs has been determined from the application of the Brunauer–Emmett–Teller method. The study allowed us to correlate the processing conditions and ditopic linker dimension to the network surface area. Both Gd-MOF and Eu-doped Gd-MOF have been tested for sensing of the inorganic ions such as Fe³⁺ and Cr₂O₇²⁻. Full article

Developing multi-selective luminescence sensing technology to differentiate serial compounds is very important but challenging. White-light-emitting decoding sensing based on lanthanide metal-organic frameworks (Ln-MOFs) is a promising candidate for multi-selective luminescence sensing application. In this work, three isomorphic Ln-MOFs based on H₃dcpcpt (3-(3,5-dicarboxylphenyl)-5-(4-carboxylphenl)-1H-1,2,4-triazole) ligand, exhibiting red, blue, and green emission, respectively, have been synthesized by solvothermal reactions. The isostructural mixed Eu/Gd/Tb-dcpcpt is fabricated via the in-situ doping of different Ln³⁺ ions into the host framework, which can emit white light upon the excitation at 320 nm. It is noteworthy that this white-light-emitting complex could serve as a convenient luminescent platform for distinguishing eight frequently-used antibiotics: five through luminescence-color-changing processes (tetracycline hydrochloride, yellow; nitrofurazone, orange; nitrofurantoin, orange; sulfadiazine, blue; carbamazepine, blue) and three through luminescence quenching processes (metronidazole, dimetridazole, and ornidazole). Moreover, a novel method, 3D decoding map, has been proposed to realize multi-selective luminescence sensing applications. This triple-readout map features unique characteristics on luminescence color and mechanism. The mechanism has been systematically interpreted on the basis of the structural analysis, energy transfer and allocation process, and peak fitting analysis for photoluminescence spectra. This approach presents a promising strategy to explore luminescent platforms capable of effectively sensing serial compounds. Full article