Lanthanide Complexes Research Articles

A Lanthanide-Based Supramolecular Nanotube and Its Photochemistry

Lanthanide complex including Europium ion (Eu3+) is one of the fascinating photoluminescent compound. However, most of lanthanide complexes are used as a mononuclear-based material without void space. Here, we developed lanthanide-based assemblies including a supramolecular nanotube. Their photophysical properties related to dynamic exciton was investigated.

Synthesis of anhydrous lanthanum acetate. Analysis of it’s structural, thermal and electronic properties

Acetate complexes of rare earth elements are extensively studied compounds known for their diverse properties and potential applications and lanthanum acetate hydrate is commercially available. In this work, a powdered anhydrous lanthanum acetate (La(CH3COO)3) sample was prepared by dissolving lanthanum oxide (La2O3) in an excess of acetic acid (CH3COOH) and distilled water (H2O), followed by direct evaporation at 150 °C. The decomposition of La(CH3COO)3 was studied, showing initiation around 300 °C and conclusion at ≥700 °C, with four distinct thermal events (I–IV) of mass loss. Gas phase identification revealed acetone and carbon dioxide as decomposition products, indicating pyrolytic decarboxylation. The final thermal effect (IV) is linked to the decomposition of La2O2CO3 to La2O3. The DFT refinement of atomic coordinates of hydrogen atoms, which were unavailable from experiment, was successfully performed. Obtained structural data was checked using vibrational spectroscopy method. The calculated electronic band structure of La(CH3COO)3 indicates it as an indirect wide band gap material with values of direct transition close to indirect. The optical bandgap is found to be 5.49 eV, suggesting that the charge transfer in La(CH3COO)3 can be optically activated with wavelengths shorter than 226 nm, which falls within the deep UV (DUV) region.

A De Novo Metalloenzyme for Cerium Photoredox Catalysis.

Cerium photoredox catalysis has emerged as a powerful strategy to activate molecules under mild conditions. Radical intermediates are formed using visible light and simple complexes of the earth-abundant lanthanide. Here, we report an artificial photoenzyme enabling this chemistry inside a protein. We utilize a de novo designed protein scaffold that tightly binds lanthanide ions in its central cavity. Upon visible-light irradiation, the cerium-dependent enzyme catalyzes the radical C-C bond cleavage of 1,2-diols in aqueous solution. Protein engineering led to variants with improved photostability and metal binding behavior. The photoenzyme cleaves a range of aromatic and aliphatic substrates, including lignin surrogates. Surface display of the protein scaffold on Escherichia coli facilitates whole-cell photobiocatalysis. Furthermore, we show that also natural lanthanide-binding proteins are suitable for this approach. Our study thus demonstrates a new-to-nature enzymatic photoredox activity with broad catalytic potential.

Sandwich‐Type Single‐Molecule Magnets Complexes of Er(III) with Ansa‐Cyclooctatetraenyl Ligands†

Comprehensive SummaryMany sandwich‐type lanthanide complexes show extremely high energy barriers (Ueff) for the reversal of magnetization and high blocking temperatures, being the star molecules in the research area of single‐molecule magnets. Herein, the preparation, structural determination, and magnetic property studies of two ansa‐bridged Er‐COT (COT = cyclooctatetraenyl dianion) complexes [KDME2][Er((η8‐COT‐SiMe2)2O)] (1) and [KDME2][Er((η8‐COT‐SiiPr2)2O)]K[Er((η8‐COT‐SiiPr2)2O)] (2) were reported. The Er(III) ions in both complexes are sandwiched by two COT rings which are ansa‐bridged by a [Si‐O‐Si] group. Magnetic studies reveal both complexes display slow magnetic relaxations with comparable energy barriers (228(5) K for 1, and 196(4) K for 2) and blocking temperatures (10.5 K for both complexes). The difference in the relaxation times (τ) for the two complexes was studied in details: different molecular vibrations induced by the substituents are the main reason for τ for 1 being about 10 times longer than for 2 at the same temperature above 10 K, while the quantum tunnelling of magnetization relaxation time (τQTM) for 2 is about 10 times longer than for 1 below 8 K, probably owing to the different dipolar interactions. Further rearrangement of molecular network with such ansa‐bridged SMMs is promising to design molecular magnetic materials with enhanced properties or new properties.

Rare earth elements sequestration in phytoliths: Partitioning patterns and influencing mechanism

Rare earth elements (REEs) are integral to numerous high-tech industries, yet their biogeochemical cycling within ecosystems remains inadequately characterized. Recently, phytoliths have been identified as potentially significant sinks for REEs; however, their role in the cycling of these elements has been underestimated. In this work, we investigate the accumulation of REEs in phytoliths (PhytREEs) within the Greater Khingan Mountains region, employing an optimized wet oxidation method combined with heavy liquid flotation to quantify PhytREEs contents in surface soils. The results revealed an elevation-dependent pattern of PhytREEs concentration, with heightened levels at higher altitudes and diminishing concentrations towards the eastern plains. The enrichment coefficient of PhytREEs (ECPhytREEs) was found to be approximately 2.7 %, indicative of a moderately selective sequestration process. The multivariate analysis indicated that terrain complexity, climatic patterns, soil texture, and organic matter significantly influence the uptake and storage of REEs in plants, subsequently affecting their partitioning in phytoliths. Among these factors, the complexation of REEs with organic matter emerged as a pivotal mechanism facilitating their immobilization within phytoliths. Soil characteristics also play a non-negligible role in modulating REEs dynamics. Our findings highlight the predominant influence of climate on PhytREE storage, suggesting that climatic variables are the primary drivers modulating the bioavailability and ultimate sequestration of REEs within phytoliths. This study enhances our understanding of the biotic-abiotic interplay in the sequestration of REEs and underscores the need to incorporate phytoliths into models of terrestrial REE cycling.

Synthesis and Reactivity of the Rare-Earth Metal Complexes Bearing the Indol-2-yl-Based NCN Pincer Ligand.

The pincer rare-earth dialkyl complexes [κ3-LRE(CH2SiMe3)2 (RE = Lu(1a), Yb(1b), Er(1c), Y(1d), Dy(1e))] with the indol-2-yl-based NCN pincer ligand were synthesized by the reactions of the proligand HL (L = 1-Me2NCH2CH2-3-(2-iPrC6H5N═CH)C8H4N) with RE(CH2SiMe3)3(THF)2. These complexes exhibited a variety of reactivities toward organic compounds such as amines, triphenylphosphine ylide, N-phenylimidazole, pyridine derivatives, and o-carborane leading to σ-bond metathesis, migration insertion, and redox reaction products. The reactions of the dialkyl rare-earth metal complexes with o-carborane afforded the novel NCN pincer-ligated carboryne-based metallacyclopropanes which reacted with diphenyl ketone to give insertion products of the RE-C2-ind and one of the RE-Ccage bonds, while the reaction of the carboryne-based metallacyclopropanes with diphenyldiazomethane produced the di-aza-metallacyclopentanes via the insertions of the N═N bond of the diphenyldiazomethane into two RE-Ccage bonds and the RE-C2-ind bond. The reactions of the dialkyl complexes with 2 equiv of 2,2'-bipyridine afforded the pincer-ligated bis(2,2'-bipyridyl monoanionic radical) complexes via the homolytic redox reaction.

Effect of Pyrrolidinedithiocarbamate Ligand on the Luminescence Properties of Heteroligand Samarium and Europium Complexes: Experimental and Theoretical Study.

The photophysical properties of two isostructural heteroligand lanthanide complexes of general formula Ln(pdtc)3(phen) (pdtc = pyrrolidinedithiocarbamate anion, phen = 1,10-phenanthroline), Ln = Sm3+ (1), Eu3+ (2)) were studied in solid state and dichloromethane (DCM) solution. The two lanthanide complexes were investigated by experimental techniques for structural (single-crystal X-ray diffraction analysis of 1, powder XRD, TG-DTA) and spectroscopic [electron paramagnetic resonance (EPR), infrared (IR), ultraviolet-visible (UV-vis), photoluminescence (PL)] characterization. DFT/TDDFT/ωB97xD and multireference SA-CASSCF/NEVPT2 calculations with perturbative spin-orbit coupling corrections were applied to construct the Jablonski energy diagrams and to discuss the excited state energy transfer mechanism with competing excited state processes and possible sensitized mechanism of metal-centered emission. The first excited state (S1) involved in the excited state energy transfer L(antenna)-to-Ln was predicted to have interligand (pdtc-to-phen) charge transfer character in contrast to the previously predicted ligand-to-metal charge transfer character. The theoretical consideration showed similar relaxation paths and luminescence quenching channels and appropriate Donor*(phen)-Acceptor*(Ln3+) energy gap for 1 and 2. The experimental measurements in the solid state, however, showed efficient luminescence and good ability to convert UV to visible light only for the Sm(pdtc)3(phen) complex. The minor emission of 2 was explained by partial reduction of Eu3+, confirmed by EPR and calculated electron density distribution data.

Covalency-Driven Differences in the Hydrogenation Chemistry of Lanthanide- and Actinide-Based Frustrated Lewis Pairs.

The electronic organization of Frustrated Lewis Pairs (FLPs) allows them to activate strong bonds in mechanisms that are usually free of redox events at the Lewis acidic site. The unique 6d/5f manifold of uranium could serve as an interesting FLP acceptor site, but to date FLP-like catalysis with actinide ions is unknown. In this paper, the catalytic, FLP-like hydrogenation reactivity of trivalent uranium complexes is explored in the presence of base-stabilized silylenes. Comparison to isoelectronic, isostructural lanthanide and thorium complexes lends insight into the electronic factors governing dihydrogen activation. Mechanistic studies of the uranium- and lanthanide-catalyzed hydrogenations are presented, including discussion of likely intermediates. Computational modeling of the f-element complexes, combined with experimental comparison to p-block Lewis acids, elucidates the relevance of steric hindrance to productive reactivity with dihydrogen. Consideration of the complete experimental and theoretical evidence provides a clear picture of the electronic and steric factors governing dihydrogen activation by these FLPs.

Rare-Earth Metallocenes for Polymerization of Olefins and Conjugated Dienes: From Fundamental Studies to Olefin Block Copolymers.

The various steps in the mechanism of olefin polymerizations mediated by neutral rare-earth metallocene complexes are discussed. The complexes are either trivalent hydride and alkyl rare-earth compounds or divalent metallocenes that are activated by the monomer via an oxidation step. The stereospecific polymerizations of conjugated dienes based on the association of a cationic metallocene complex and an alkylaluminum and the polymerization mechanism based on monomer insertion into an aluminum-carbon bond are also discussed. The exploitation of metallocene complexes for the copolymerization of olefins with conjugated dienes is the subject of a third part of this review. The synthesis of new elastomers called ethylene butadiene rubber (EBR) is highlighted. Finally, the use of rare-earth metallocenes in macromolecular engineering is detailed. This includes the synthesis of functional polyolefins and block copolymers including thermoplastic elastomers.

Template syntheses, molecular structures, and antimicrobial activities of two novel Schiff-base macrocyclic lanthanide complexes

Template syntheses, molecular structures, and antimicrobial activities of two novel Schiff-base macrocyclic lanthanide complexes

Design and photophysical characterization of dinuclear lanthanide complexes incorporating spacer ligands along with their mononuclear analogues: A comparative study

Two heteroleptic homo-dinuclear complexes of Dy(III) and Sm(III) with pyrazine (pyz) as spacer ligand [Ln(TFPB)3(μ-pyz)Ln(TFPB)3], along with their mononuclear analogue [Ln(TFPB)3(pyz)2] were synthesized and characterized. Diketone TFPB (4,4,4-trifluoro-1-phenyl-1,3-butanedione) was incorporated as main ligand. NMR analysis depicted single peak for pyz protons for dinuclear complexes and two for mononuclear ones, which confirmed the bridging nature of pyz in former complexes. UV spectra revealed two absorption bands despite of the different metal ion and nuclearity of complex, suggesting the absorption of UV-radiation by coordinated moieties inspite of the metal ion involved. The emission spectra exhibited significant intensity of yellow and orange-red peaks for Dy(III) and Sm(III) complexes, respectively, indicating effective sensitization of metal center. The enhanced emission intensity observed in dinuclear Sm-complexes, compared to their mononuclear counterparts, indicates a synergistic effect of the two metal ions on the overall emission properties, rather than a mere additive effect that would be expected from two independent mononuclear units. The photoluminescent properties of synthesized complexes were examined and discussed, suggesting potential applications in display devices. The Correlated Color Temperature (CCT) of these complexes falls within a range suitable for warm light sources and the highest branching ratio observed for 4G5/2 → 6H9/2 (for Sm3+ ion) and 4F9/2 → 6H13/2 (for Dy3+ ion) transitions suggests potential application in laser amplification. The alignment between band gap measurements obtained from UV and CV analyses highlight the possibility of employing these complexes in semiconductor technologies.

Synthesis, characterization, anticancer, antibacterial, antioxidant, DFT, and molecular docking of novel La (III), Ce (III), Nd (III), and Dy (III) lanthanide complexes with Schiff base derived from 2‐aminobenzothiazole and coumarin

Four novel lanthanide La (III), Ce (III), Nd (III), and Dy (III) complexes with (Z)‐4‐(benzo[d]thiazol‐2‐ylamino)‐3‐((benzo[d]thiazol‐2‐ylimino)methyl)‐2H‐chromen‐2‐one (L) were prepared and characterized. The novel compounds' structural compositions were elucidated by the application of analytical and spectroscopic methodologies. From physical and chemical measurements, the general formula for the [LnLCl3]2H2O complexes (C1‐C4) was proposed, which was proven by theoretical measurements. Using cisplatin, gentamicin, ampicillin, and ascorbic acid as standards, the compound's anticancer, antibacterial, and antioxidant qualities were assessed, and activities followed the order: Ce (III)L(C2) > Nd (III)L(C3) > Dy (III)L(C4) > La (III)L(C1) > L where the Ce (III) complexes exhibited the highest activity followed by Nd (III) complexes. Molecular docking studies were performed using the MOA2022 software to identify putative binding mechanisms for the methionine adenosyl‐transferases in liver cancer (PDB ID: 5A19) and the most active site of the Bacillus subtilis receptor (PDB ID: 5e6k), where the strength of the interaction increases with the negative binding energy L ˂ [LaLCl3] ˂ [DyLCl3] ˂ [NdLCl3] ˂ [CeLCl3].

Innovative hybrid and bifunctional rare earth complexes as corrosion inhibitors for AA2024 Alloy: Electrochemical and surface analysis enhanced by DFT/MD simulation

The hybrid inorganic–organic compounds, RE-thioglycolates (RE = Ce, Nd, Sm), were analyzed as effective green corrosion inhibitors of AA2024 alloy in 0.1 M NaCl solution. Utilizing Electrochemical Impedance Spectroscopy the protective inhibitory film on the alloy’s surface was affirmed, alongside the persistence of a natural oxide layer over time. These complexes demonstrated notable corrosion inhibition efficiency over immersion from 1 h to 3 days, with Sm-thiog retaining the high inhibition efficiency of over 95 % during 72 h. All RE-thioglycolates are mixed-type inhibitors, imparting resistance against both general and pitting corrosion.The presence of a protective inhibitory film on the AA2024 surface in NaCl solution has been substantiated through various analytical techniques including FTIR, SEM/EDS and XPS. A detailed examination of the differential inhibition exhibited by these bifunctional complexes is elucidated through theoretical calculations. The smallest difference of HOMO and LUMO orbitals for Sm-thiog of 3.21 eV indicates that this inhibitor attains the strongest donor–acceptor interactions with the metal surface. Predictions generated by Density Functional Theory/Molecular Dynamics simulations suggest the potential formation of diverse inhibitory species within the electrolyte. The corrosion inhibition mechanism proposed for RE-thioglycolates is grounded in electrochemical and theoretical insights, and subsequently validated through surface analysis methods.

Highly transparent and stable luminescent films with stable europium (III) complex Assisted with anti-Reflective coating

Rare earth complex polymer luminescent materials have important practical application value in organic electroluminescence, fluorescence sensing, solar cells and other fields. Herein, we fabricated the luminescent film (recorded as Eu (2 mCND)4Na/PMMA@LF) through doped Eu (2 mCND)4Na complex with polymethyl methacrylate (PMMA) followed by coating on a PMMA slab. And the antireflective (AR) coatings prepared with acid-catalyzed silica sol (ACSS) and base-catalyzed silica sol (BCSS) were coated on the surface of Eu (2 mCND)4Na/PMMA@LF which enhance its transparency increasing from 92 % to 98.7 %. This is because that the AR coatings have high transmittance and environmental stability. In addition, the luminescent film coated with antireflective coating displays high photo-stability, which was also demonstrated after a 35 h UV LED (∼200 mW/cm2) irradiation. The configuration of luminescent film with anti-reflection performance provides a scalable alternative to the current approaches for creating highly transparent solar windows.

Lanthanoid Semiquinonate/Tropolonate Complexes: Redox Chemistry and Luminescence

AbstractHeteroleptic lanthanoid (Ln = Eu, Gd, Tb, Dy, Ho and Yb) complexes featuring hydro‐tris(1‐pyrazolyl)borate (Tp−) ligands combined with the bidentate O‐donor ligands tropolonate (trop−) or 3,5‐di‐tertbutylseminquinonate (dbsq⋅−) have been synthesized and investigated. Despite the similarity of the bidentate O‐donor trop− and dbsq⋅− ligands, and the lanthanoid coordination geometries, the complexes [LnTp2dbsq] (Ln‐dbsq) and [LnTp2trop] (Ln‐trop) exhibit markedly different redox and photophysical properties. The electrochemistry of Ln‐dbsq is dominated by processes associated with the readily redox‐active dbsq⋅− moiety. In contrast, the relative redox inactivity of Ln‐trop allows for the observation of the Eu(III) to Eu(II) reduction process. Photophysical measurements reveal no sensitized emission for the Ln‐dbsq family, while the trop− antenna ligand is able to sensitize emission in the visible range for Eu(III) and Ho(III), and in the near‐infrared for Ho(III) and Yb(III).

Light-responsive multimode luminescence in photochromism transparent wood for anti-counterfeiting application

With the rapid development of information technology, people’s security awareness of information protection is enhanced, and the requirements for anti-counterfeiting technology have become higher and higher on different occasions. Smart materials with light stimulus response have attracted extensive attention in the development of anti-counterfeiting materials, especially next-generation intelligent transparent wood. Inspired by the color-changing behavior of plants and animals in nature, a photochromic transparent wood (PTW) composite with light-stimulated response was prepared by compounding rare earth luminescent complexes with transparent wood (TW). PTW exhibits high transmittance (85.5 %). Moreover, PTW exhibits different optical states under different light conditions, namely, colorless under sunlight and bright red fluorescence under 365-nm UV light, and the process is reversible. Additionally, PTW patterned by laser etching offered greater flexibility and personalization in terms of stimulus-response, and its information security under different light stimuli is demonstrated. Meanwhile, the PTW prepared can be applied to different products and their packaging as an invisible anti-counterfeiting label, and the storage and protection of information is realized under visible light, and the decoding of information is implemented in UV light, so as to achieve the invisible anti-counterfeiting of information. More importantly, invisible information can be clearly identified even in black packaging. The design concepts and techniques of this study provide an inspiration to combine smart responsive materials with wood-based materials to develop intelligent responsive materials, and also provides support for the subsequent design and preparation of invisible anti-counterfeiting materials.

Facile conjugate electro-spinning to achieve nanofiber yarns with concurrent color-tunable photoluminescence and tailored superparamagnetism

In this work, we have successfully fabricated hetero-structured nanofiber yarns (NFYs) with a conjugate electro-spinning technique, integrating a dual-functional capability of tunable color photoluminescence and tailored superparamagnetism. These hetero-structured NFYs are comprised of [Eu(BA)3phen + Tb(BA)3phen]/polyacrylonitrile (PAN) photoluminescent nanofibers (NFs) and Fe3O4/PAN superparamagnetic NFs, which allow for the effective isolation of dark-colored Fe3O4 nanoparticles (NPs) from rare earth complexes. This design leads to enhanced photoluminescent performance for the hetero-structured NFYs. Detailed investigations into the morphologies and performances of these NFYs were conducted using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), fluorescence spectrophotometry, and vibrating sample magnetometry (VSM). The emitting light color, ranging from red to yellow to green, can be tuned under a specific excitation wavelength (276 nm) of ultraviolet (UV) light by regulating the proportion of rare earth complexes. Furthermore, the superparamagnetism of the NFYs can be tailored by varying the amounts of Fe3O4 NPs. The designing philosophy and preparative technique can be utilized to manufacture other polyfunctional nanomaterials.

Research progress in circularly polarized luminescence properties of rare earth complexes

Research progress in circularly polarized luminescence properties of rare earth complexes

Transparent Luminescent down-conversion coating for improved performance and enhanced stability of carbon-based perovskite solar cells

Methylammonium lead halide-based perovskite solar cells (PSCs) perform superior photovoltaic performance, nevertheless, demonstrate limited light utilization and instability within the ultraviolet (UV) range. Lanthanide-based down-conversion (DC) materials can mitigate the photoinduced deterioration by resolving spectrum mismatched losses. Particularly, lanthanide complexes possess a broad UV absorbing region thus can convert absorbed UV light to visible or near-infrared light, exhibiting large pseudo-Stoke's shift while they could allow spectrum responsiveness of the PSCs in the UV.Therefore, the DC material may enhance the photovoltaic performance by converting high-energy photons to low-energy photons whilst may also perform as UV shielding material, and finally may both develop PSCs' efficiency and stability. Herein, a novel transparent luminescent down-converting layer (LDC) based on a highly emitting Europium complex in a siloxane matrix was used as an external coating to PSCs with the purpose of improving the solar cells' performance extending their response in the UV region while improving cells’ photostability. The conducted studies indicated that the LDC coating may additionally serve as an anti-reflective and UV-shielding layer simultaneously, resulting in better light-harvesting ability of the perovskite. As a result, short circuit current (Jsc) amplification by the presence of LDC re-emitting the absorbed UV light to the visible and the best carbon-based perovskite solar cell (C-PSC) revealed a 16.13 % overall performance in comparison to the 15.38 % obtained for the control device. Furthermore, photostability tests demonstrated that the unencapsulated LDC-modified devices prepared under ambient conditions retained 75 % of their initial PCE after 8 h under artificial solar light illumination whereas the control devices remained at 40 % at the same conditions. These findings suggest that the LDC layer decreases the UV degradation for PCEs, resulting in PCE and stability enhancement.

Spectrophotometric Method for Studying the Stability of Late Lanthanide Complexes

Spectrophotometric Method for Studying the Stability of Late Lanthanide Complexes