Lanthanide Complexes Research Articles

Cycloheptatrienyl-Bridged Triple-Decker Complexes.

The first structurally characterized organometallic multidecker sandwich complexes featuring a cycloheptatrienyl ring (Cht, C7H73-) in the coordination sphere are presented. The synthesis of inverse sandwich complexes of the rare earth elements YIII and ErIII with a bridging cycloheptatrienyl ligand of the type [(thf)(BH4)2LnIII(μ-η7:η7-Cht)LnIII(BH4)(thf)2] is described first. The subsequent introduction of the CotTIPS ligand (CotTIPS = 1,4-(iPr3Si)2C8H62-) into the coordination sphere of the rare earth cations resulted in the isolation of unprecedented triple-decker compounds with the formula [(thf)3K{(η8-CotTIPS)LnIII}2(μ-η7:η7-Cht)], bearing a seven-membered aromatic carbon ring as a middle deck. These compounds are also the first examples of rare earth triple-decker complexes not bridged by a Cot derivative, based on purely carbon-based ligands. The magnetic properties of the respective ErIII congeners were investigated in detail, leading to the observation of antiferromagnetic coupling of the ErIII cations and a blocking temperature of 13.5 K. The conversion of the YIII compound [(thf)3K{(η8-CotTIPS)YIII}2(μ-η7:η7-Cht)] with [YIII(Cot)I(thf)2] resulted in ligand rearrangement and the selective formation of the first triple-decker complex ([(η8-CotTIPSYIII)2(μ-η8:η8-Cot)]) featuring two Cot ligands with different substituents in its coordination sphere.

Sensitively detection of ascorbic acid in orange samples with ionic liquid functionalized carbon dots and lanthanide complexes

In the food industry, ascorbic acid (AA) is widely used as an antioxidant. However, the concentration of AA is influenced by various factors, including temperature, time, and pH value during food preparation and storage, leading to its instability in content. This makes the accurate detection of AA content particularly important. Precise determination of AA content in food and pharmaceuticals is crucial for ensuring the adequate intake of essential vitamins and maintaining good health. Herein, we have developed a successful preparation method of an imidazole-based ionic liquid functionalized CDs hybrids APM-CDs. A novel photo functional hybrid probe Eu3+@APM-CDs was obtained via an ion-exchange reaction between APM-CDs and lanthanide complex Eu(DPA)3. The obtained hybrid probe was extensively characterized in detail. What's more, the results show that the fluorescent intensity of Eu3+@APM-CDs has a good linear response to AA concentrations in the range of 25–500 μM (R2 = 0.99), with a detection limit of 80 nM. The fluorescence probe demonstrates good selectivity and sensitivity toward AA and has the potential for significant application in AA detection by simplifying procedures and reducing interference from impurities.

Design and synthesis of Lanthanide(III) complex based luminescence probes for time-resolved luminescence detection of β-galactosidase

β-Galactosidase (β-Gal), confirmed to provide energy and participate in the galactosyl transfer reaction, is primarily over-expressed in ovarian cancer cells. Herein, detecting endogenous β-Gal is essential for the diagnosis and monitoring of primary ovarian cancer cells. In this study, we proposed two structurally related cationic Lanthanide(III) triamide complexes for highly sensitive and rapid detection of β-Gal. Moreover, LDEu02 showed a low detection limit (2.3 × 10−3 U/mL) and high specificity with high affinity for β-Gal, which had great potential to the detection of the β-Gal activity by using time-resolved fluorescence techniques.

2.2]Paracyclophanes: From Selective Functionalization to Optical Properties

AbstractSince their discovery, [2.2]paracyclophane (pCp) and its derivatives have fascinated the scientific community due to their original molecular architecture and unusual electronic behavior. Over the years, significant efforts have been devoted to the development of substituted pCps for a variety of applications in different fields, ranging from organic synthesis and asymmetric catalysis to polymer chemistry and material science. This review describes a series of useful approaches that allow chemists to selectively decorate pCps, control the planar chirality that these molecules can display as soon as they are functionalized, and tune their photophysical behaviors. For each of these aspects of paracyclophane chemistry, selected examples of major advances are presented, and possible directions for future research are outlined. The application of pCp as central core for the development of uncommon 3D luminophores is finally highlighted. Emphasis is placed on the potential use of planar chiral luminescent paracyclophanes as antennas or ligands for the design of multifunctional lanthanide complexes, a quite underdeveloped but highly promising area for future research endeavors.

Dual lanthanide Complexes-Loaded ratiometric nanothermometer for elucidating intracellular variations of temperature and calcium transport

Herein, we report a ratiometric nanothermometer to study the correlation of heat/temperature and intracellular calcium transport. Firstly, poly(methyl methacrylate)-based copolymeric nanoparticles (NPs) from nanoprecipitation encapsulates two lanthanide complexes (Eu(DNPD)3Phen and Sm(DBM)3Phen) to enhance fluorescence of lanthanide ions (Ln3+). NPs were thereafter coated with an amphiphilic block copolymer pluronic F-127 to prevent nonspecific interaction between NPs and proteins, which ensures internalization of the nanothermometer into living cells. The back energy transfer (BET) from the excited state of Ln3+ to the triplet energy levels of ligand endows the temperature dependence on ratiometric fluorescence of Eu3+ and Sm3+. This nanothermometer has excellent anti-interference ability, ensuring accurate cell temperature measurement within a range of 29.0–40.0℃. It exhibits a maximum relative thermal sensitivity of 1.9 % ℃-1 at 29.0℃ and a minimum temperature resolution of 0.1℃ at 39.0℃ in live HeLa cells. The nanothermometer was applied for studying temperature or heat induced intracellular Ca2+ transport. It illustrated that free cytoplasmic Ca2+ concentration ([Ca2+]i) increased only when the cell temperature reached a certain threshold under photothermal stimulation, and the rise of temperature corresponds to the increase of [Ca2+]i. Furthermore, Ca2+ burst induced Ca2+ transport from cytoplasm to endoplasmic reticulum, which promoted ATP hydrolysis along with the rise of intracellular temperature. 200 s stimulation with FCCP enhanced ca. 1.7℃ of intracellular temperature along with 2.2 folds increment of [Ca2+]i, as FCCP induces Ca2+ efflux from mitochondria by increasing proton concentration therein. These results indicate that a close relationship between intracellular temperature and Ca2+ transport, which is of great significance for further understanding the role of temperature in signaling pathways and neurotransmitter release events.

Harnessing redox-inactive rare-earth metals for photocatalytic reductive coupling of benzyl bromides

Compared with rare and expensive late-transition metals, rare-earth photocatalysts are much less investigated in synthetic chemistry, particularly concerning redox-inactive rare-earth metals. Herein, we describe a general strategy to realize the redox-inactive rare-earth photocatalysis by grafting a light-absorbing scaffold onto common ligands in rare-earth organometallics. Three guanidinate rare-earth complexes with photocatalytic functions were synthesized and found to exhibit higher catalytic efficiency than phenothiazine in the reductive homocoupling of benzyl bromides. These preliminary results illustrated that our “grafting” strategy could serve as a facile methodology for the construction of redox-inactive rare-earth photocatalysis systems.

Preparation and Application of Time-Resolved Fluorescent Nanospheres (TRFNs) for Immunochromatography of Ferritin

Time-resolved fluorescent nanospheres (TRFNs) are polymer nanospheres with special functional groups on the surface loaded with rare earth complexes which emit fluorescence when irradiated by ultraviolet light. TRFNs offer spherical morphology, homogeneity, good dispersity, large specific surface area, easy chemical modification, high loading capacity and good biocompatibility. The rare earth complexes possess unique properties that render them highly sensitive and capable of effectively excluding unspecific fluorescence. Hence, they constitute an excellent labeling material for the time-resolved fluorescence immunochromatographic assay (TRFIA). The developed method has a linear response to ferritin from 6 to 1000 ng/mL with a detection limit of 3.5 ng/mL, good reproducibility, and good accuracy compared with commercial chemiluminescence measurements of serum. These results suggest that the reported TRFN has utility for time-resolved fluorescence immunochromatographic assays.

Color-tunable fluorescence and ultralong organic room temperature phosphorescence from multicomponent copolymers

Materials with color-tunable photoluminescence (PL) have attracted dramatically increasing interest in recent years, especially the tuning of both fluorescence (FL) and ultra-long organic room temperature phosphorescence (UOP). Herein, a series of polymer films are successfully fabricated by in situ copolymerization of carbazole derivatives, lanthanide complex, and acrylamide (AM). With a long lifetime of 2.82 s and a high quantum yield of 21.40%, these copolymers exhibit not only color-tunable FL from violet-red to blue, but also multicolor UOP scope from blue to chartreuse when the excitation wavelength is changed. Moreover, a nearly-white phosphorescence can also be observed by adjusting the excitation wavelength. Multiple information patterns with color-tunable FL and UOP emissions are captured, exhibiting promising potential in the information encryption and anti-counterfeiting fields.

Synthesis and Reactivity of Bis-tris(pyrazolyl)borate Lanthanide/Aluminum Heterobimetallic Trihydride Complexes.

Molecular heterobimetallic hydride complexes of lanthanide (Ln) and main-group (MG) metals exhibit chemical properties unique from their monometallic counterparts and are highly reactive species, making their synthesis and isolation challenging. Herein, molecular Ln/Al heterobimetallic trihydrides [Ln(Tp)2(μ-H)2Al(H)(N″)] [2-Ln; Ln = Y, Sm, Dy, Yb; Tp = hydrotris(1-pyrazolyl)borate; N″ = N(SiMe3)2] have been synthesized by facile insertion of aminoalane [Me3N·AlH3] into the Ln-N amide bonds of [Ln(Tp)2(N″)] (1-Ln). Thus, this is a simple synthetic strategy to access a range of Ln/Al hydrides. Reactivity studies demonstrate that 2-Ln is a heterobimetallic hydride, with evidence for the cooperative nature of 2-Ln shown by the catalytic amine-borane dehydrocoupling under ambient conditions in contrast to its monomeric counterparts.

Luminescence of Lanthanide Complexes in Mesoporous Silica Matrices: A Textbook Example of Tris‐Dipicolinate Europium Complex Adsorbed in SBA‐15

AbstractThe incorporation of luminescent lanthanide complexes in inorganic matrices opens appealing possibilities in the rational upstream conception of new luminescent materials with easier recyclability. In this regard, the influence of SBA‐15 mesoporous silica, as a host matrix, on the photophysical properties of europium‐trisdipicolinate cesium salt is investigated. The lanthanide complex can be completely and reversibly adsorbed on the silica, using incipient wetness impregnation (IWI) in WATER, without the need of anchoring groups or covalent bonding on the silica surface. This specific procedure allows the homogeneous dispersion of the lanthanide complex into the host silica matrix. Appropriately assessing the photophysical properties of the targeted luminescent material proved remarkably challenging, demanding utmost caution, particularly due to the strong scattering of the mesoporous matrices. Additionally, while the observations confirm an important increase of luminescence lifetimes of lanthanide complexes upon integration into these mediums, this variation is attributed to the differing refractive indexes and not to specific surface interactions or confinement effect. Indeed, it appeared that previous literature precedents depicted erroneous exhalations of the complexes intrinsic quantum yield due to the repeated use of erroneous refractive index values. In the meantime, the luminance of these materials under UV irradiation improves drastically in comparison to what is obtained with the physical dispersion of micro‐crystals of the lanthanide complex onto silica. It is demonstrated that this improvement is due to a reduced inner filter effect in the adsorbed samples. In this regard, IWI of lanthanide complexes in the mesoporous matrices method could be of interest in the development of recyclable emitting layers, less demanding in terms of emitter quantity.

Unexpected Supramolecular-Induced Redox Switching in Sandwich Gd Bisphthalocyaninate.

The redox state of the phthalocyanine in sandwich lanthanide complexes is crucial for their applications. In this work, we demonstrate that the cation-induced supramolecular assembly of crown-substituted phthalocyanine lanthanide complexes Ln[(15C5)4Pc]2 can be used to control the redox state of the ligand simultaneously with the coordination sphere of the central metal. We achieve unprecedented redox switching of phthalocyanine ligands in a double-decker Gd(III) complex, resulting from the intramolecular inclusion of potassium cations between the decks with simultaneous twisting of the ligands (the skew angle between them decreases from 44.61 to 0.21°). Such a structural change leads to an increase in the deck-to-deck distance and drastically facilitates ligand reduction. This process was shown to be anion-dependent: only potassium salts of weak acids (KOPiv and KOAc) induce intramolecular inclusion of cations with redox switching in contrast to salts of strong acids (KBr, KOPic, KSCN, and KPF6), where such a redox process does not occur. This breakthrough opens new avenues for controlling the electrochromic properties, of phthalocyanines, along with other properties, such as electrical conductivity, optics, etc.

Synthesis and preservation performance of lanthanum-tannin complex from Cercis glabra Pampan

This article explores the feasibility of rare earth element-tannin complexes as a wood preservative. The tannins (T) from Cercis glabra Pampan. are extracted, sulfonated (ST), and coordinated with lanthanum (La) elements to fabricate the complexes (La-T, and La-ST). Results show that two stable complexes, La-T and La-ST, are successfully formed by coordinating the La-ions with the phenolic hydroxyl groups in T and ST. Sulfonated tannins have a better adsorption capacity for lanthanum ions. The mass percentage of La in La-ST (36.50%) is higher than that in La-T (24.85%). The results of the white-rot decay test reveal that wood treated with La-T (1.98%) and La-ST (2.58%) preservatives has significantly lower weight loss rates compared to the untreated (28.94%). However, the brown rot decay test demonstrates that wood treated with La-T (62.68%) and La-ST (50.81%) only has slightly lower weight loss rates compared to the untreated (71.84%). Finally, the leaching of La-T and La-ST treated poplar wood was significantly lower than La self-treated ones. This novel approach can produce stable rare earth-wood preservatives and improve the wood's bio-durability and anti-leaching properties, thus remarkably enhancing the outdoor performance of modified wood products.

Dy4 and Dy5 complexes based on tautomeric hydrazone Schiff-base ligand regulated by temperature showing single-molecule magnet behaviour

Two dysprosium complexes [Dy4(H2L)6]⋅4H2O (Dy4) and [Dy5(H2L)(HL)2(L)(µ3OH)2Cl(H2O)(MeCN)2]⋅4MeOH⋅7H2O (Dy5) (H4L = (N',N'''E,N',N'''E)-N',N'''-(pyridine-2,6-diylbis(methanylylidene))bis(2-hydroxybenzohydrazide)) based on hydrazone Schiff-base ligand were synthesized, which could be regulated by controlling temperature (Dy4, below 293 K and Dy5, over 308 K). Magnetic studies show that complex Dy4 is a typical field-induced single-molecule magnet with an effective energy barrier (Ueff) of 42.9 K under 1 kOe dc field. Complex Dy5 is a zero dc field single-molecule magnet with an effective energy barrier (Ueff) of 4.18 K. The results indicate the synthesis of lanthanide complexes is sensitive to substitute of ligand and temperature.

Rare-Earth Metal Complexes Supported by A Tridentate Amidinate Ligand: Synthesis, Characterization, and Catalytic Comparison in Isoprene Polymerization.

To systematically investigate the dependence of the initiating group and metal size on polymerization performance, a family of rare-earth metal bis(alkyl)/bis(benzyl)/bis(amide) complexes supported by a monoanionic tridentate amidinate ligand [(2,6-iPr2C6H3)NC(Ph)N(C6H4-2-OMe]- (HL) were synthesized and well-characterized. Treatment of rare-earth metal tris(alkyl)/tris(benzyl)/tris(amide) complexes Y(CH2C6H4NMe2-o)3 or Y(CH2SiMe3)3(THF)2 or Ln[N(SiHMe2)2]3(THF)x (Ln = Sc, x = 1; Ln = Y, La, Sm, Lu, x = 2) with 1 equiv of HL gave the corresponding mono(amidinate) rare-earth metal bis(alkyl)/bis(benzyl)/bis(amide) complexes [(2,6-iPr2C6H4)NC(Ph)N(C6H4-2-OMe)]Y(CH2C6H4NMe2-o)2 (1), [(2,6-iPr2C6H4)NC(Ph)N(C6H4-2-OMe)]Y(CH2SiMe3)2(THF) (2), and [(2,6-iPr2C6H4)NC(Ph)N(C6H4-2-OMe)]Ln[N(SiHMe2)2]2(THF)n (Ln = Y, n = 1 (3); Ln = La, n = 1 (4); Ln = Sc, n = 0 (5); Ln = Lu, n = 0 (6); Ln = Sm, n = 0 (7)) in good isolated yields. These complexes were characterized by elemental analysis, NMR spectroscopy, and single-crystal X-ray diffraction. In the presence of excess AlMe3 and on treatment with 1 equiv of [Ph3C][B(C6F5)4], these complexes could serve as precatalysts for cationic polymerization of isoprene, in which the dependence of the polymerization activity and regioselectivity on the initiating group and metal size was observed.

Understanding the separation of trivalent lanthanides and actinides using multiple diglycolamide-containing ligands: a review

Abstract The complexation and separation behaviour of trivalent actinides and lanthanides with various multiple diglycolamide (DGA) group-containing ligands are compiled in the present review. The DGA arms are anchored on various scaffolds, viz., C- and N-pivot tripodal backbones, benzene-centred tripodal backbones, calix[4]arene, pillar[5]arene and azamacrocycle scaffolds. Dendrimers of different generations having DGA arms were also evaluated for the extraction and complexation studies of trivalent actinide and lanthanide ions. The extraction efficiency of the DGA units increases significantly when they are grouped together on a single backbone/scaffold. Furthermore, the selectivity was found to improve in many cases, particularly with respect to the UO2 2+ ion. This is very important for the development of suitable ligands for the extraction/separation of the actinide and lanthanide ions. Combined experimental, luminescence and DFT studies on the complexation of trivalent actinides and lanthanides with these DGA-based ligands are quite useful to understand their extraction and separation behaviour and this review article gives a critical analysis of the results available in the literature.

Engineering Clock Transitions in Molecular Lanthanide Complexes.

Molecular lanthanide (Ln) complexes are promising candidates for the development of next-generation quantum technologies. High-symmetry structures incorporating integer spin Ln ions can give rise to well-isolated crystal field quasi-doublet ground states, i.e., quantum two-level systems that may serve as the basis for magnetic qubits. Recent work has shown that symmetry lowering of the coordination environment around the Ln ion can produce an avoided crossing or clock transition within the ground doublet, leading to significantly enhanced coherence. Here, we employ single-crystal high-frequency electron paramagnetic resonance spectroscopy and high-level ab initio calculations to carry out a detailed investigation of the nine-coordinate complexes, [HoIIIL1L2], where L1 = 1,4,7,10-tetrakis(2-pyridylmethyl)-1,4,7,10-tetraaza-cyclododecane and L2 = F- (1) or [MeCN]0 (2). The pseudo-4-fold symmetry imposed by the neutral organic ligand scaffold (L1) and the apical anionic fluoride ion generates a strong axial anisotropy with an mJ = ±8 ground-state quasi-doublet in 1, where mJ denotes the projection of the J = 8 spin-orbital moment onto the ∼C4 axis. Meanwhile, off-diagonal crystal field interactions give rise to a giant 116.4 ± 1.0 GHz clock transition within this doublet. We then demonstrate targeted crystal field engineering of the clock transition by replacing F- with neutral MeCN (2), resulting in an increase in the clock transition frequency by a factor of 2.2. The experimental results are in broad agreement with quantum chemical calculations. This tunability is highly desirable because decoherence caused by second-order sensitivity to magnetic noise scales inversely with the clock transition frequency.

Using Chiral Auxiliaries to Mimic the Effect of Chiral Media on the Structure of Lanthanide(III) Complexes Common in Bioimaging and Diagnostic MRI.

[Ln·DOTA]- complexes and systems derived therefrom are commonly used in MRI and optical bioimaging. These lanthanide(III) complexes are chiral, and, in solution, they are present in four forms, with two sets of enantiomers, with the ligand donors arranged in either a square antiprismatic, SAP, or twisted square antiprismatic geometry, TSAP. This complicated speciation is found in laboratory samples. To investigate speciation in biological media, when Ln·DOTA-like complexes interact with chiral biomolecules, six Eu·DOTA-monoamide complexes were prepared and investigated by using 1D and 2D 1H NMR. To emulate the chirality of biological media, the amide pendant arm was modified with one or two chiral centers. It is known that a chiral center on the DOTA scaffold significantly influences the properties of the system. Here, it was found that chirality much further away from the metal center changes the available conformational space and that both chiral centers and amide cis/trans isomerism may need to be considered─a fact that, for the optically enriched materials, led to the conclusion that eight chemically different forms may need to be considered, instead of the four forms necessary for DOTA. The results reported here clearly demonstrate the diverse speciation that must be considered when correlating an observation to a structure of a lanthanide(III) complex.

On-Surface Synthesis of Organolanthanide Sandwich Complexes.

The synthesis of lanthanide-based organometallic sandwich compounds is very appealing regarding their potential for single-molecule magnetism. Here, it is exploited by on-surface synthesis to design unprecedented lanthanide-directed organometallic sandwich complexes on Au(111). The reported compounds consist of Dy or Er atoms sandwiched between partially deprotonated hexahydroxybenzene molecules, thus introducing a distinct family of homoleptic organometallic sandwiches based on six-membered ring ligands. Their structural, electronic, and magnetic properties are investigated by scanning tunneling microscopy and spectroscopy, X-ray absorption spectroscopy, X-ray linear and circular magnetic dichroism, and X-ray photoelectron spectroscopy, complemented by density functional theory-based calculations. Both lanthanide complexes self-assemble in close-packed islands featuring a hexagonal lattice. It is unveiled that, despite exhibiting analogous self-assembly, the erbium-based species is magnetically isotropic, whereas the dysprosium-based compound features an in-plane magnetization.

Synthesis, structure, fluorescence and magnetic studies of two oxygen bridged polycarboxylic acid ligands and rare earth metal ion Pr, Gd, and Er complexes

In order to further enrich the research on the synthesis of complexes with polycarboxylic acid ligands and rare earth metal ion. In this study, four rare earth complexes, namely, [Gd(cpia)]n (1), [Er(cpia)]n (2), [Pr(cpna)2·2H2O]n (3) and [Gd(Hcpna)(cpna)•3H2O]n (4) have been synthesized by solvothermal method based on 5-(2-carboxyphenoxy)isophthalic acid (H3cpia) and 5-(4-carboxyphenoxy)nicotinic acid ligand (H2cpna) with rare earth metal ions Pr3+, Gd3+ and Er3+. Single crystal X-ray diffraction analyses reveal that complexes 1, 2 and 3 are two-dimensional network structure, 4 is one-dimensional chain structures. The fluorescence test results show that the fluorescence intensity of complexes 1 and 2 were lower than that of the H3cpia ligand, the fluorescence intensity of complexes 3 and 4 were lower than that of the H2cpna ligand. Magnetic results indicate complex 1 has ferromagentic behavior and weak antiferromagentic behavior in the complexes 2, 3 and 4.

Augmentation of NIR Circularly Polarized Luminescence Activity in Shibasaki-Type Lanthanide Complexes Supported by the Spirane Sphenol.

We report two new circularly polarized luminescence (CPL)-active lanthanide complexes emissive in the near-infrared (NIR) region; using sphenol as a supporting ligand, we provide the first reported example of an NIR-emissive lanthanide complex supported by a chiral spirane. Inclusion of a quaternary carbon to impart axial chirality results in dramatic augmentation of the CPL strength of the resultant sphenolate complexes (glum ≤ 0.77 for [(sphenol)3ErNa3(thf)6]) compared to that of their contemporary biaryl-based axially chiral analogues (glum ≤ 0.47 for [(binol)3ErNa3(thf)6]). Despite similar structural parameters, the rigid spiro carbon of sphenol enables the strongest dissymmetry factors observed to date from Shibasaki-type complexes for both Yb and Er. We also demonstrate the sensitivity of the reported chiroptical measurements to small variations in instrumental parameters, such as bandpass, and suggest a standardized method or at least that additional detail should be included in future reports to allow for direct comparisons between newly published CPL emitters.