Lanthanide Complexes Research Articles

Fabrication of lanthanide complexes in metal-organic frameworks as self-calibrating temperature sensor

Temperature plays an important role as a physical parameter in industry and science, it is crucial to measure temperature accurately. Herein, by “ship-in-a-bottle” strategy, Ln(phen) (Ln = Eu3+, Tb3+; phen = 1,10-phenanthroline) was successfully prepared in one-dimensional pores of Na–Zn-MOF. With the lanthanide co-doping approach, EuxTb1-x(phen)@Na–Zn-MOF (3–7@Na–Zn-MOF) were achieved. The luminescent properties of EuxTb1-x(phen)@Na–Zn-MOF revealed systematic tuning of their luminescent colors from green, through yellow to red with increasing Eu3+ doping concentration. Interestingly, two fluorescence emission peaks of 5@Na–Zn-MOF at 544 nm and 617 nm demonstrate different fluorescence responses to temperature, exhibiting self-calibrating sensor in the range of 293–373 K with the supreme relative sensitivity of 11.02 %·K−1 at 373 K. Moreover, its luminescent color changes from yellow (293 K) to red (373 K), representing suitable as colorimetric luminescent sensor. Furthermore, 5@Na–Zn-MOF was blended with poly(vinylidene fluoride) (PVDF) to produce a mixed-matrix membrane (MMM), which also shows excellent temperature response accompanied by color changing.

Synergy of Experiment and Broadened Exploration of Ab Initio Calculations for Understanding of Lanthanide-Pentacyanidocobaltate Molecular Nanomagnets and Their Optical Properties.

We present a synergistic experimental-theoretical methodology for the investigation of lanthanide-based single-molecule magnets (SMMs), demonstrated using the example of novel heterometallic molecules incorporating Nd3+/Ce3+ ions combined with three different, rarely explored, pentacyanidocobaltate(III) metalloligands, [CoIII(CN)5(azido/nitrito-N/iodido)]3-. The theoretical part of our approach broadens the exploration of ab initio calculations for lanthanide(III) complexes toward the convenient simulations of such physical characteristics as directional dependences of Helmholtz energy, magnetization, susceptibility, and their thermal and field evolution, as well as light absorption and emission bands. This work was conducted using newly designed SlothPy software (https://slothpy.org). It is introduced as an open-source Python library for simulating various physical properties from first-principles based on results of electronic structure calculations obtained within popular quantum chemistry packages. The computational results were confronted with spectroscopic and ac/dc-magnetic data, the latter analyzed using previously designed relACs software. The combination of experimental and computational methods gave insight into phonon-assisted magnetic relaxation mechanisms, disentangling them from the temperature-independent quantum tunneling of magnetization and emphasizing the role of local-mode processes. This study provides an understanding of the changes in lanthanide(III) magnetic anisotropy introduced with pentacyanidocobaltates(III) modifications, theoretically exploring also potential applications of reported compounds as anisotropy switches or optical thermometers.

Surface complexation of rare earth elements on goethite in sea-floor hydrothermal environment: Insight from first principles simulations

Deep-sea mud shows tremendous resource potential for rare earth elements (REEs) and its formation is closely associated with sea-floor hydrothermal activities. Iron (oxyhydr)oxides link the sources and sinks of REEs in sea-floor hydrothermal systems. However, the complexation mechanisms of REEs on iron (oxyhydr)oxides have not been well understood yet. In this study, by using the first principles molecular dynamics technique, we first calculated the pKa’s of surface groups on goethite (110) surface at elevated temperatures relevant to sea-floor hydrothermal systems and then evaluated the complexation structures and free energies of REEs on goethite (110) and (010) surfaces using the method of constraint by taking Sc3+, Y3+, and La3+ as model REE cations. The results show that REE complexation occurs in mildly acidic to neutral conditions. The most thermodynamically stable complexes of REEs are bidentate complexes on two neighboring FeOH sites on goethite (110) surface and tridentate complexes on two neighboring FeOH sites plus one Fe2OH site on goethite (010) surface. Sc3+ complexes match the goethite lattice and can be incorporated into the lattice. The stabilities of REE complexes increase with the distance from hydrothermal vents. Complexation of Y3+ is less favored on goethite compared to other REEs whereas Sc3+ prefers complexation on goethite (010) surface and La3+ exhibits similar stabilities on both (010) and (110) surfaces. The derived atomic level complexation mechanisms would be helpful for the interpretation of experimental data and the prediction of REEs’ behavior in the sea-floor. The findings presented here provide valuable insights into REEs fractionation and enrichment in deep-sea muds.

Imidobis(tetraphenylphosphinato)lanthanoid(III) complexes: Synthesis by oxidative protolysis, and redox transmetallation/protolysis, structural studies and Hirshfeld surface analysis

Redox protolysis of [YbCp2(dme)] (dme = 1,2-dimethoxyethane) by imidotetraphenyldiphosphinate, ({Ph2PO}2NH) LH yields [YbCp{(Ph2PO)2N}2}(MeCN)] 1 and [Yb{(Ph2PO)2N}3] 2 with the last also obtained by oxidative protolysis of Yb(C6F5)2. The complexes [Ln{(Ph2PO)2N}3] ((Ln = Yb 2, Er 3, Gd 4), [Sm{(Ph2PO)2N}3(MeCN)3] 5 and [Nd{(Ph2 PO)2N}3] 6 have all been prepared by redox transmetallation/protolysis reactions between Yb, Er, Gd, Sm or Nd metals, bispentafluorophenylmercury and proligand LH. Complex 1 is formally eight coordinate with an acetonitrile, cyclopentadienyl (Cp) and two chelating O,O′-(Ph2PO)2N ligands, with the MeCN trans to the Cp ring. Complexes 2 and 4·C7H8 are six coordinate monomers with three chelating O,O′ diphosphinate ligands. By contrast 5 is a highly symmetrical nine-coordinate monomer with three acetonitrile and three chelating O,O′-L ligands. The three-dimensional Hirshfeld surface (3D-HS) analysis and the two-dimensional fingerprint plots (2D-FP) were quantified for different intermolecular interactions in complexes 2 and 4.

Migration and controlling factors of rare earth elements in geothermal systems on the southern Tibetan Plateau

Rare earth elements (REE) serve as effective tracers of water-rock interactions, a crucial process in the evolution of geothermal systems. However, the geochemical behavior of REE during their migration within geothermal systems, particularly the fractionation mechanism, remains poorly understood. In this study, we focus on the geochemical characteristics of REE in hot springs, host rocks, and sinters from various hot spring systems in the Yadong-Gulu rift (YGR), the largest extensional rift in the southern Tibetan Plateau. The objective is to explore the factors that control REE concentrations in hot springs and elucidate the fractionation of REE during their migration. The concentrations of REE are significantly influenced by pH, Fe oxides (oxyhydroxides), and HCO3− concentrations in central and southern hot springs, whereas high reservoir temperatures contribute to higher ΣREE concentrations in northern hyperthermal springs. REE speciation calculations show that LnO2− and LnO2H are dominant complexes in northern alkaline hot springs, while carbonate complexes (LnCO3+ and Ln(CO3)2−) prevail in central and southern spring samples. Additionally, weakly acidic hot springs exhibit a prevalence of Ln3+, LnF2+, and LnSO4+ species. The chondrite-normalized REE patterns of all hot spring samples display enrichment in MREE, which is significantly distinct from the patterns observed in host rocks and sinters enriched in LREE. The fractionation of REE in the YGR hot spring systems is primarily controlled by the following processes: (1) Temperature, pH, and relative abundance of complexing agents influence the complexation of REE and further regulate their fractionation in hot springs; (2) During water-rock interaction, preferential leaching of HREE and MREE from host rocks can lead to their enrichment in alkaline hot springs. The dissolution of iron-rich sediments plays a significant role in generating the distinctive MREE bulge pattern in acid-neutral hot springs compared to host rocks; (3) The higher stability of MREE and HREE complexes in water, as well as the preferential coprecipitation of unstable LnCO3+ complexes formed by LREE with carbonates, are key factors responsible for LREE enrichment in sinters.

DNA binding studies and in-vitro anticancer studies of novel lanthanide complexes

Pancreatic cancer, is an aggressive type of cancer and the most common malignancy with a poor prognosis regarding metastatic disease (survival < 10 %). The development of Novel chemotherapeutic drugs holds significant prospects for practical applications. Here, this work focuses on the interaction between two lanthanide complexes, Yb-BZA and Er-BZA, with DNA, as well as their anticancer activity against pancreatic cancer. The relationship between complexes and DNA is revealed by fluorescence, absorption spectral titration, cyclic voltammetric (CV) experiments, indicating that the Yb-BZA and Er-BZA interact with FS-DNA by bind groove. Moreover, molecular docking technology was utilized to confirm the binding of Yb-BZA and Er-BZA with 1BNA and 4AV1. The cytotoxic effects of Yb-BZA and Er-BZA on cancer cells BxPC-3 were evaluated, Yb-BZA (IC50 = 6.459 μg/mL) is more effective than oxaliplatin (IC50 = 16.46 μg/mL) evaluated using cytotoxicity assay. Yb-BZA and Er-BZA has the potential to become a chemotherapy drug for pancreatic cancer cells.

Application of the Adiabatic Connection Random Phase Approximation to Electron-Nucleus Hyperfine Coupling Constants.

The electron-nucleus hyperfine coupling constant is a challenging property for density functional methods. For accurate results, hybrid functionals with a large amount of exact exchange are often needed and there is no clear "one-for-all" functional which describes the hyperfine coupling interaction for a large set of nuclei. To alleviate this unfavorable situation, we apply the adiabatic connection random phase approximation (RPA) in its post-Kohn-Sham fashion to this property as a first test. For simplicity, only the Fermi-contact and spin-dipole terms are calculated within the nonrelativistic and the scalar-relativistic exact two-component framework. This requires to solve a single coupled-perturbed Kohn-Sham equation to evaluate the relaxed density matrix, which comes with a modest increase in computational demands. RPA performs remarkably well and substantially improves upon its Kohn-Sham (KS) starting point while also reducing the dependence on the KS reference. For main-group systems, RPA outperforms global, range-separated, and local hybrid functionals─at similar computational costs. For transition-metal compounds and lanthanide complexes, a similar performance as for hybrid functionals is observed. In contrast, related post-Hartree-Fock methods such as Møller-Plesset perturbation theory or CC2 perform worse than semilocal density functionals.

Unusually Large Ligand Field Splitting in Anionic Europium(III) Complexes Induced by a Small Imidazolic Counterion.

Luminescent trivalent lanthanide (Ln3+) complexes are compounds of technological interest due to their unique photophysical properties, particularly anionic tetrakis complexes, given their higher stability and emission quantum yields. However, structural studies on the cation-anion interaction in these complexes and the relation of such to luminescence are still lacking. Herein, the cation-anion interactions in two luminescent anionic tetrakis(2-thenoyltrifluoroacetonato)europate(III) complexes with alkylimidazolium cations, specifically 1-ethyl-3-methylimidazolium and 1-butyl-3-methylimidazolium are investigated. The Eu3+ complexes were synthesized and characterized by elemental analysis, mass spectrometry, and single-crystal X-ray crystallography, and their luminescence spectra were recorded at 77 K. Quantum chemical calculations were also performed. X-ray crystallography revealed hydrogen bonds between the enolate ligands and imidazolium ring hydrogens. The 1-butyl-3-methylimidazolium complex had two crystallographic Eu3+ sites, also confirmed by luminescence spectroscopy. The 1-ethyl-3-methylimidazolium complex exhibited an unusual 300 cm-1 splitting in the 5D0 → 7F1 transition, as reproduced by ligand field calculations, suggesting a stronger hydrogen bonding due to the smaller substituent. We hypothesize that this strong bonding likely causes angular distortions, resulting in high ligand field splittings.

Lanthanide Complexes Based on Rigid Benzimidazole Carboxylic Acid Ligand: Sensing of Nitrobenzene, Fe(III) Ions, and Adsorption of Dyes

ABSTRACTFive new lanthanide complexes {[Sm(H2L)(H2O)4(Cl)]⋅H2O⋅Cl}n (1), {[Eu(H2L)(H2O)4Cl]⋅Cl}n (2), {[La(H2L)(H2O)4Cl]⋅Cl}n (3), {[Pr(H2L)(H2O)4Cl]⋅Cl}n (4), {[Ce(H2L)(H2O)4Cl]⋅Cl}n (5) (H3L = 2‐hydroxy‐5‐(5‐(hydroxy‐λ2‐methoxy)‐1H‐benzo[d]imidazole‐5‐carboxylic acid) were successfully synthesized under solvothermal method. 1 exhibits a two‐dimensional (2D) network structure, whereas 2–5 feature one‐dimensional (1D) chain structure. The fluorescence investigations demonstrated that 1–5 could be the fluorescent sensor for nitrobenzene (NB) and Fe(III) ions with high selectivity, sensitivity, and low detection limits. Furthermore, 1–5 displayed the good adsorption to anionic dye Congo red (CR), and the adsorption capacities were 140.5, 206.5, 212.5, 111.5, and 211.5 mg·g−1, respectively.

Triple-Decker Hexaazamacrocyclic Lanthanide(III) Complexes: Structure, Magnetic Properties, and Temperature-Dependent Luminescence.

The reaction of fluoride anions with mononuclear rare-earth(III) complexes of the hexaazamacrocycle derived from 2,6-diformylpyridine and ethylenediamine affords trinuclear coordination compounds [Ln3L3(μ2-F)4(NO3)2](NO3)3. The X-ray crystal structures of these complexes show triplex cationic complexes where the three roughly parallel macrocyclic lanthanide(III) units are linked by bis-μ2-F bridges. The detailed analysis of the photophysical properties of the [Eu3L3(μ2-F)4(NO3)2](NO3)3·2H2O and [Tb3L3(μ2-F)4(NO3)2](NO3)3·3H2O complexes reveals different temperature dependence of luminescence intensity and luminescence decay time of the Eu(III) and Tb(III) derivatives. The spectra of mixed species of average composition [Eu1.5Tb1.5L3(μ2-F)4(NO3)2](NO3)3·3H2O are in accordance with the ratiometric luminescent thermometer behavior. Measurements of the direct-current (dc) magnetic susceptibility of the [Dy3L3(μ2-F)4(NO3)2](NO3)3·2H2O complex indicate possible ferromagnetic interactions between the Dy(III) ions. Alternating current (ac) susceptibility measurements of this complex indicate single-molecule magnet behavior in zero dc field with magnetic relaxation dominated by Orbach mechanism and an effective energy barrier Ueff = 12.3 cm-1 (17.7 K) with a pre-exponential relaxation time, τ0 of 7.3 × 10-6 s. A similar reaction of mononuclear macrocyclic complexes with a higher number of fluoride equivalents results in polymeric {[Ln3L3(μ2-F)5](NO3)4}n complexes. The X-ray crystal structure of the Nd(III) derivative of this type shows trinuclear units that are additionally linked by single fluoride bridges to form a linear coordination polymer.

Spectroscopic Studies of Lanthanide(III) Complexes with L-Malic Acid in Binary Systems.

Binary systems of lanthanide ions (La, Nd, Gd, Ho, Tb, and Lu) with L-malic acid in molar ratios of 1:1 and 1:2 were studied. This study was carried out in aqueous solutions, and the composition of the formed complexes was confirmed using computer data analysis. The overall stability constants of the complexes and the equilibrium constants of the reaction were determined. The effect of ligand concentration on the composition of the internal coordination sphere of the central atom was observed. Changes in the coordination sphere of lanthanide ions were confirmed by spectroscopic measurements.

A new strategy for the preparation of polylactic acid composites with UV resistance, light conversion, and antibacterial properties

A novel rare earth complex, Eu(IAA)2(phen)2 (EuIP), was synthesized by solution-based synthesis method. Then, EuIP and polylactic acid (PLA) were melt-blended at 190 °C to obtain a multifunctional PLA/EuIP composite. The incorporation of EuIP provided PLA/EuIP composites with good light conversion ability. Under UV irradiation, PLA/EuIP composites converted the absorbed UV light into red light. Moreover, the PLA/1.0EuIP composite exhibited excellent light transmittance of 88 % in the visible region and showed strong red emission under UV light. After UV irradiation for 96 h, the molecular weights and mechanical properties of neat PLA decreased dramatically. Interestingly, the molecular weights and mechanical properties of PLA/EuIP composites did not deteriorate after 96 h of UV irradiation. The reason was that EuIP could absorb UV light and utilize the absorbed energy to emit red fluorescence. Furthermore, PLA/EuIP composites showed good antibacterial activities against E. coli and S. aureus. In addition, in vitro cell experiments showed that PLA/EuIP composites was suitable for the growth of murine breast cancer (4 T1) cells. Besides, enzymatic degradation testing also proved that PLA/EuIP composites had good biodegradability. This work provides an ingenious design strategy for the preparation of PLA/EuIP composites possessing light conversion ability, UV resistance, and antibacterial properties.

Photochromic Spiropyran-Based Dual-Emitting Luminescent Hybrid Films for Dynamic Information Anticounterfeiting.

Photoluminescent materials are widely used for information storage and anticounterfeiting, while most of them have the disadvantages of static information performance and weak processability, which is still a challenging task in developing dynamic anticounterfeiting materials with high security levels. Herein, we fabricated a novel photostimuli-responsive dual-emitting luminescent material UPTES-SPn-Tb-hfa, which was obtained by introducing the photochromic molecule spiropyran (SP) and lanthanide complex (Tb-hfa) into a siloxane-polyether matrix using the sol-gel process. Due to the conformation-dependent photochromic fluorescence resonance energy transfer between the Tb-hfa donor and SP acceptor, the ring-closing (SP)/ring-opening (MC) isomerization of the SP unit leads to a reversible luminescence switching in UPTES-SPn-Tb-hfa. This composite material has great potential for advanced anticounterfeiting because of the advantage of rapidly repeatable encryption/decryption for at least 8 times and dynamic luminescent colors within 15 s. In addition, due to its two luminescent centers (Tb3+ and MC), the luminescent color of this material can be regulated by 254 and 365 nm UV-light irradiation, which facilitates the design of multicolored anticounterfeiting labels. Our work presents a novel design methodology to fabricate dynamic anticounterfeiting materials, significantly enhancing the security of anticounterfeiting applications.

Unearthing the Real-Time Excited State Dynamics from Antenna to Rare Earth Ions Using Ultrafast Transient Absorption.

The conventional energy transfer pathway in organic lanthanide complexes is purported to be from the excited singlet state of the chromophore to the triplet state and subsequently directly to the emitting state of the trivalent lanthanide ion. In this work, we found that the energy transfer occurs from the triplet state to the nearest energy level, instead of directly to the emitting state of the lanthanide ion. The triplet decay rate for different lanthanide ions follows an energy gap law from the triplet level to the receiving level of the lanthanide ion. Three different categories of complexes were synthesized and inspected using different techniques, demonstrating the universality of our findings. This work renews the insights to conventional findings, highlighting the importance of the energy gap between the triplet state and the nearest lanthanide energy level in optimization of light harvesting. The rationale of ligand design of chromophores should be reconsidered, leading to various applications of lanthanide complexes with enhanced quantum yield and brightness.

Syntheses, structures and magnetisms of dimethyl phosphate-bridged dinuclear lanthanide complexes with pentadentate macrocyclic ligand

A series of air-stable dinuclear complexes, [HNEt3]2[Ln2(L)2((CH3O)2PO2)4](BPh4)4 (L = 2,14-dimethyl-3,6,10,13,19-pentaazabicyclo[13.3.1]nonadeca1(19), 2,13,15,17-pentene, Ln = Dy, 1-Dy; Tb, 2-Tb; Gd, 3-Gd), has been synthesized and characterized using single-crystal X-ray crystallography and magnetic measurements. The crystal structures disclose that two dimethyl phosphate anions act as bridging ligands, linking two Ln(III) ions. Each Ln(III) ion is eight-coordinated by five nitrogen atoms from a pentadentate Schiff based ligand L and three oxygen atoms from three dimethyl phosphates, forming a triangular dodecahedral coordination geometry. Direct-current magnetic susceptibility measurements indicate an extremely weak antiferromagnetic exchange between Gd(III) ions in 3-Gd. Complex 1-Dy exhibits slow magnetic relaxation with an effective energy barrier (Ueff) of 13 K under an applied field of 1000 Oe, whereas 2-Tb does not exhibit single-molecule magnet behavior. This work presents a novel strategy for constructing polynuclear single-molecular magnets by using a pentadetate macrocycle as magnetic building blocks integrated with replaceable axial ligands.

Fluorescence array sensor based on lanthanide complex for pattern recognition detection of fluoroquinolone antibiotics

Fluoroquinolone antibiotics, a class of animal and human useful antibiotics, are widely utilized in numerous fields including biomedical science, animal husbandry, and aquatic finfish farming. Its high demand and wide application have directly or indirectly led to substantial consumption and discharge of antibiotics, affecting not only the environment but also endangering human health through bioaccumulation. Hence, rapid and precise detection of trace antibiotics in water, food, and biological samples is critically important. This research synthesized Tb3+/Eu3+ complexes with dual emission centers, and a fluorescence sensor array was constructed with the fluorescence intensity ratio F1/F2 of the two emission centers as a signal. Different sensitization effect of fluoroquinolone antibiotics towards lanthanide complexes aided in differentiating five fluoroquinolone antibiotics from two others. Additionally, the sensor array can effectively detect fluoroquinolone antibiotics in real samples, suggesting its reliability and practicality of complex sample analysis. The excellent qualitative and quantitative analysis ability of this strategy for fluoroquinolone antibiotics offers a novel perspective for antibiotic residue detection, showcasing a new opportunity for lanthanide complex application in sensor arrays.

Bis(phosphinophenyl)amido-Ligated Binuclear Rare-Earth Metal Complexes for Highly cis-1,4-Selective Polymerization of 1,3-Conjugated Dienes.

A series of binuclear rare-earth metal complexes based on the ligands containing bis(phosphinophenyl)amido-PNP unit are successfully synthesized. All the ligands and the corresponding binuclear complexes are fully characterized by NMR spectra (1H, 13C, and 31P). In conjunction with [Ph3C][B(C6F5)4], all the binuclear complexes exhibited high catalytic activity and high cis-1,4-selectivity (>99%) toward the polymerization of 1,3-conjugated dienes (isoprene, β-myrcene and β-farnesene) with excellent livingness at room temperature or even 80°C.

Synthesis and Characterization of Folic Acid-Conjugated Terbium Complexes as Luminescent Probes for Targeting Folate Receptor-Expressing Cells.

Several conjugates between folic acid and a series of kinetically stable lanthanide complexes have been synthesized, using amide coupling and azide-alkyne cycloaddition methodologies to link the metal-binding domain to folate through a variety of spacer groups. While all these complexes exhibit affinity for the folate receptor, it is clear that the point of attachment to folate is essential, with linkage through the γ-carboxylic acid giving rise to significantly enhanced receptor affinity. All the conjugates studied show affinities consistent with displacing biological circulating folate derivatives, 5-methyltetrahydrofolate, from folate receptors. All the complexes exhibit luminescence with a short-lived component arising from ligand fluorescence overlaid on a much longer lived terbium-centered component. These can be separated using time-gating methods. From the results obtained, the most promising approach to achieve sensitized luminescence in these systems requires incorporating a sensitizing chromophore close to the lanthanide.

Toward liquid cell quantum sensing: Ytterbium complexes with ultranarrow absorption.

The energetic disorder induced by fluctuating liquid environments acts in opposition to the precise control required for coherence-based sensing. Overcoming fluctuations requires a protected quantum subspace that only weakly interacts with the local environment. We report a ytterbium complex that exhibited an ultranarrow absorption linewidth in solution at room temperature with a full width at half maximum of 0.625 milli-electron volts. Using spectral hole burning, we measured an even narrower linewidth of 410 pico-electron volts at 77 kelvin. Narrow linewidths allowed low-field magnetic circular dichroism at room temperature, used to sense Earth-scale magnetic fields. These results demonstrated that ligand protection in lanthanide complexes could substantially diminish electronic state fluctuations. We have termed this system an "atomlike molecular sensor" (ALMS) and proposed approaches to improve its performance.

Crystal Engineering of Three Novel 1-D Chalcogenidostannates Using Lanthanide Complexes as Structure-Directing Agents: Synthesis, Structure, and Photoelectric Performance Evaluation

Crystal Engineering of Three Novel 1-D Chalcogenidostannates Using Lanthanide Complexes as Structure-Directing Agents: Synthesis, Structure, and Photoelectric Performance Evaluation