Lanthanide Centers Research Articles

Pyrazine Dicarboxylic Acid and Phosphite-Bridging Lanthanide-Incorporated Tellurotungstates and Their Fluorescence Performances.

Two pyrazine dicarboxylic acid and phosphite-bridging lanthanide-incorporated tellurotungstates [H2N(CH3)2]12 Na4[Ln4(H2O)2(H2PDBA)2(HPO3)2W6O10][B-α-TeW8O31]4 · 70H2O [Ln = Eu3+ (1), Tb3+ (2); H2PDBA = 2,5-pyrazine dicarboxylic acid) were prepared, which contain four [B-α-TeW8O31]10- subunits and a deca-nuclear heterometallic [Ln(H2O)2(HPO3)2 (H2PDBA)2(W3O5)2]24+ cluster. Strikingly, two H2PDBA ligands connect two equivalent {W3Eu2O5(H2O)(B-α-TeW8O31)2(HPIIIO3)}8- moieties to form the polyanion skeleton, while the phosphite plays a bridging role in joining two lanthanide centers in the {W3Eu2O5(H2O)(B-α-TeW8O31)2(HPIIIO3)}8- moiety. In addition to the fluorescence (FL) properties of 1 and 2 at room temperature, their temperature-dependent FL properties were also investigated. In 80-298 K, FL intensities of 1 and 2 decrease as temperature increases, and their maximum relative sensitivities (Sr) are 3.70 and 1.99% K-1, whereas the minimum temperature uncertainties (δT) are 1.25 and 1.18 K for 1 and 2. In 298-973 K, upon increasing temperature, FL intensities of 1 and 2 initially rise to their maxima at 373 K and subsequently decrease. This is because samples of 1 and 2 undergo dehydration together with amorphization below 473 K and decomposition above this temperature. This work lays a foundation for the development for luminescent thermometers based on lanthanide-incorporated polyoxometalates.

Elucidating Polyphosphate Anion Binding to Lanthanide Complexes Using EXAFS and Pulsed EPR Spectroscopy.

Reversible anion binding to lanthanide complexes in aqueous solution has emerged as an effective method for anion sensing. Through careful design of the organic ligand, luminescent lanthanide complexes capable of binding biologically relevant anions in a bidentate or monodentate manner can be realized. While single-crystal X-ray diffraction analyses and NMR spectroscopy have revealed the structural geometry of several host-guest complexes, the challenge remains in designing preorganized lanthanide receptors with enhanced anion selectivity for broader applications in diagnostics and bioimaging. To address this challenge, innovative and complementary methods to investigate host-anion binding geometry are becoming increasingly important. Herein, we demonstrate the combined use of Eu L3-edge extended X-ray absorption fine structure (EXAFS) and electron paramagnetic resonance (EPR) spectroscopy to elucidate the binding of nucleoside phosphates (ATP, ADP, and AMP) to a cationic lanthanide complex. We establish that ATP unequivocally binds the lanthanide center in a bidentate manner in water, while ADP adopts both bidentate and monodentate modes, and AMP binds in a monodentate manner. This interdisciplinary approach provides deeper insight into lanthanide host-guest chemistry in solution, laying the groundwork for designing emissive probes that undergo specific anion-induced structural changes and elicit desired optical responses upon binding.

Lanthanide Complexes Containing a Terminal LnIII−O Bond: Hydrolysis as a Tool to Assess f‐Element Bond Covalency

AbstractWe report the preparation, isolation, and reactivity of gas‐phase lanthanide nitrate and acetate complexes featuring the elusive trivalent LnIII=O bond. Complexes [LnIII(O)(X)2]− (X=NO3− or CH3CO2−; Ln=La, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Tm, Lu) are prepared from [LnIII(CH3CO2)(X)3]− precursors through decarboxylation followed by nitromethane or acetone elimination. The oxo complexes hydrolyze at rates indicating LnIII=O bond stability. The rates for [LnIII(O)(NO3)2]− are essentially invariant, whereas those for [LnIII(O)(CH3CO2)2]− exhibit a moderate decrease across the lanthanide series. The kinetics of lanthanide‐oxo bond hydrolysis are assessed in the context of participation of 5d2 electrons in bonding, changes in covalency via variations in 5d orbital energies and radial extensions, and steric crowding around the lanthanide center. The observed fast hydrolysis rates and lack of correlation to electronic and qualitative covalent considerations confirm the expected strong polarization in LnIII=O bonding, with variations in covalency minimally impacting reactivity. The LnIII=O bond reactivity is compared with previous results for LnIII−O⋅ and LnIV=O, and actinide AnIII=O and AnIV=O; implications for lanthanide/actinide and lanthanide/lanthanide partitioning are discussed. Additionally, nitromethane and acetone elimination are demonstrated as useful for inducing a 2e− O‐atom transfer resulting in non‐oxidative formation of lanthanide‐oxos.

Indole-derivative β-diketone samarium and terbium compounds modified by ancillary ligand: Syntheses, crystal structures, and photoluminescence properties

EIFD, LnCl3·6H2O (Ln = Sm, Tb) and ancillary ligand are developed to synthesize a sequence of six new β-diketone Sm-based and Tb-based compounds modified to enhance the photoluminescence property, namely Sm(EIFD)3(H2O)·CH2Cl2 (1), Sm(EIFD)3(bpy) (2), Sm(EIFD)3(phen)·CH2Cl2 (3), Tb(EIFD)3(H2O)·CH2Cl2 (4) and Tb(EIFD)3(bpy) (5), Tb(EIFD)3(phen)·CH2Cl2 (6) (EIFD: 1-(1-ethyl-1H-indol-3-yl)-4,4,4-trifluorobutane-1,3‑dione, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline). The crystal structures of compounds 1−6 with the lanthanide(III) ions of seven (1, 4)/eight (2, 3, 5, 6) coordinated configuration are determined by single-crystal X-ray diffraction. Different non-covalent interactions (NCIs) and their% contribution to the compounds structures and their roles in stabilizing the structure are determined by Hirshfeld surface analysis. The photoluminescence properties of compounds 1−6 by substituting the solvent H2O with bpy and phen contained nitrogen ancillary ligands are then studied experimentally, leading to a rationalization of their central lanthanide(III) ions emission lifetime.

Chiral Star-Shaped [CoIII3LnIII] Clusters with Enantiopure Schiff Bases: Synthesis, Structure, and Magnetism.

Two enantiomeric pairs of new 3d-4f heterometallic clusters have been synthesized from two enantiomer Schiff base derivatives: (R/S)-2-[(2-hydroxy-1-phenylethylimino)methyl] phenol (R-/S-H2L). The formulae of the series clusters are Co3Ln(R-L)6 (Ln = Dy (1R), Gd (2R)), Co3Ln (S-L)6 (Ln = Dy (1S), Gd (2S)), whose crystal structures and magnetic properties have been characterized. Structural analysis indicated that the above clusters crystallize in the chiral P213 group space. The central lanthanide ion has a coordination geometry of D3 surrounded by three [CoIII(L)2]- anions using six aliphatic oxygen atoms of L2- featuring a star-shaped [CoIII3LnIII] configuration. Magnetic measurements showed the presence of slow magnetic relaxation with an effective energy barrier of 22.33 K in the DyIII derivatives under a zero-dc field. Furthermore, the circular dichroism (CD) spectra of 1R and 1S confirmed their enantiomeric nature.

Evaluation of Point Group Symmetry in Lanthanide(III) Complexes: A New Implementation of a Continuous Symmetry Operation Measure with Autonomous Assignment of the Principal Axis.

The structure of molecular systems dictates the physical properties, and symmetry is the determining factor for all electronic properties. This makes group theory a powerful tool in quantum mechanics to compute molecular properties. For inorganic compounds, the coordination geometry has been estimated as idealized polyhedra with high symmetry, which, through ligand field theory, provides predictive capabilities. However, real samples rarely have ideal symmetry, and although continuous shape measures (CShM) can be used to evaluate deviation from an ideal reference structure σideal, this often fails for lanthanide(III) complexes with high coordination numbers, no obvious choice of principal axes, and no obvious reference structure. In lanthanide complexes, the unique electronic structures and associated properties are intricately tied to the symmetry around the lanthanide center. Therefore, robust methodologies to evaluate and estimate point group symmetry are instrumental for building structure-property relationships. Here, we have demonstrated an algorithmic approach that orients a molecular structure Q in the best possible way to the symmetry axis of any given point group G and computes a deviation from the ideal symmetry σsym(G,Q). This approach does not compute the deviation from an ideal reference system, but the intrinsic deviation in the structure induced by symmetry operations. If the structure contains the symmetry operation, there is no deviation and σsym(G,Q) = 0. The σsym deviation is generated from all of the symmetry operation ÔS in a point group G using the most correct orientation of the sample structure in each group G. The best orientation is found by an algorithm that minimizes the orientation of the structure with respect to G. To demonstrate the methodology, we have investigated the structure and symmetry of 8- and 9-coordinated lanthanide(III) aqua complexes and correlated the luminescence from 3 europium(III) crystals to their actual symmetry. To document the methodology, the approach has been tested on 26 molecules with different symmetries. It was concluded that the method is robust and fully autonomous.

Coercive Fields Exceeding 30 T in the Mixed-Valence Single-Molecule Magnet (CpiPr5)2Ho2I3.

Mixed-valence dilanthanide complexes of the type (CpiPr5)2Ln2I3 (CpiPr5 = pentaisopropylcyclopentadienyl; Ln = Gd, Tb, Dy) featuring a direct Ln-Ln σ-bonding interaction have been shown to exhibit well-isolated high-spin ground states and, in the case of the Tb and Dy variants, a strong axial magnetic anisotropy that gives rise to a large magnetic coercivity. Here, we report the synthesis and characterization of two new mixed-valence dilanthanide compounds in this series, (CpiPr5)2Ln2I3 (1-Ln; Ln = Ho, Er). Both compounds feature a Ln-Ln bonding interaction, the first such interaction in any molecular compounds of Ho or Er. Like the Tb and Dy congeners, both complexes exhibit high-spin ground states arising from strong spin-spin coupling between the lanthanide 4f electrons and a single σ-type lanthanide-lanthanide bonding electron. Beyond these similarities, however, the magnetic properties of the two compounds diverge. In particular, 1-Er does not exhibit observable magnetic blocking or slow magnetic relaxation, while 1-Ho exhibits magnetic blocking below 28 K, which is the highest temperature among Ho-based single-molecule magnets, and a spin reversal barrier of 556(4) cm-1. Additionally, variable-field magnetization data collected for 1-Ho reveal a coercive field of greater than 32 T below 8 K, more than 6-fold higher than observed for the bulk magnets SmCo5 and Nd2Fe14B, and the highest coercive field reported to date for any single-molecule magnet or molecule-based magnetic material. Multiconfigurational calculations, supported by far-infrared magnetospectroscopy data, reveal that the stark differences in magnetic properties of 1-Ho and 1-Er arise from differences in the local magnetic anisotropy of the lanthanide centers.

Synthesis, characterization, and biological activity of some lanthanide complexes with (E)-N'-(3,5- di-tert-butyl-2-hydroxybenzylidene)picolinohydrazide: Solid-state molecular structure of [DyL(NO3)DMF]2

A series of lanthanide(III) complexes containing Schiff base ligand, [NEt3]2[Ln2(L)2(NO3)4]⋅xH2O {Ln, x: La,1; Pr, 2, Nd, 1; Sm, 1; Eu, 1; Gd, 1; Tb, 2; Dy, 2; and Er, 4; H2L: (E)-N'-(3,5-di-tert-butyl-2-hydroxybenzylidene)picolinohydrazide Schiff Base Ligand}, have been synthesized by reaction of H2L with Ln(NO3)3⋅xH2O salts {Ln, x: La, 6; Pr, 6; Nd, 6; Sm, 6; Eu, 5; Gd, 6; Tb, 5; Dy, 6; Er, 5} in the presence of Et3N. The structures of these compounds have been characterized by elemental analysis, thermal gravimetric, molar conductivity, and different spectral analysis techniques (IR, UV–vis, 1H, and 13CNMR ). Each unit of the anionic part comprises one Ln3+ ion, one bi-basic L2− ligand, and two bidentate nitrate NO3− groups. Each Ln3+ ion is coordinated by one pyridyl N atom, two alkoxido O atoms, one azomethine N atom, and one phenolate O atom. The lanthanide centers in the dinuclear core are bridged by two alkoxide groups from two ligands. The molar conductivity results have indicated that each of these complexes is a 2:1 electrolyte. Dy_L complex obtained from a mixture of MeCN/DMF solution has also been structurally characterized via X-ray diffractometry. The solid-state structure of the Dy_L complex revealed that the asymmetric unit of Dy_L is formulated from Dy3+ ion, one L2− ligand, one bi-dentate nitrate NO3− group, and one coordinated DMF molecule. The results of antioxidant activities have shown that all investigated complexes are more efficient in quenching DPPH• than the free H2L. Antibacterial activities have also been investigated against some Gram-negative bacteria and Gram-positive bacteria. The MIC values have reflected that all complexes have moderate antibacterial activity against the examined Gram-negative bacteria. On the contrary, they are inactive against the examined Gram-positive bacteria.

Synthesis, structure, and magnetic properties of lanthanide(III) complexes incorporating a tris-chelate cobalt(III) complex as a metalloligand

A series of CoIII–LnIII–CoIII trinuclear complexes [Ln{Co(Hmtimn)3}2](NO3)3 were prepared by following a simple one-pot synthesis method, mixing an unsymmetrical bidentate ligand 2-(2-imidazolinyl)-6-methoxypheol (H2mtimn) with Co(NO3)2·6H2O and LnX3· 6H2O (where Ln = La, Ce, Pr, Nd, Gd or Dy and X = NO3 − or Cl−) in methanolic solution in the presence of triethylamine in air. In the reaction mixture, this leads to the in situ formation of a tris-chelate CoIII metalloligand unit, which can coordinate LnIII ions through the interactions of phenolato- and methoxy-O donors. X-ray structural analysis revealed that the CoIII metalloligand functions as a rigid tripodal ligand to coordinate to a LnIII ion by six oxygen donors. The two metalloligands in the complex exhibit homochiral aggregation (ΔΔ or ΛΛ) upon coordination to the LnIII ion. The coordination of the central LnIII ion was found to be a distorted icosahedral geometry. Magnetic susceptibility measurements reveal that both cobalt and central lanthanide ions exist in trivalent states.

Synthesis, spectroscopic properties, crystal structure and Hirshfeld surface analysis of Pr(III), Sm(III), Gd(III), Dy(III), and Ho(III) coordination compounds with Schiff base ligand derived from 4-aminoantipyrine

Under reflux condition five new lanthanide coordination compounds, [Pr(L)2(NO3)3(CH3OH)] (1), [Sm(L)2(NO3)3(CH3OH)] (2), [Gd(L)2(NO3)3(CH3OH)] (3), [Dy(L)2(NO3)3(CH3OH)] (4) and [Ho(L)2(NO3)3(CH3OH)] (5), were synthesized in methanol where L is the Schiff base ligand prepared from the reaction of 4-aminoantipyrine and 5-bromosalicylaldehyde. Elemental analysis, FT-IR, UV/Vis and photoluminescence spectroscopic methods and single crystal X-ray analysis were used to investigate the crystal structure and properties of the synthesized compounds. Using X-ray analysis, it was found that all crystals are isomorphous and the Ln ion (Ln = Pr, Sm, Gd, Dy and Ho) in all of the synthesized compounds is nine-coordinated and the geometry around them is slightly distorted tricapped trigonal prism. Six oxygen atoms are coordinated to the central lanthanide atom by three nitrate groups, one oxygen atom from the methanol group and two oxygen atoms of the Schiff base ligand (L) which create the LnO9 coordination environment. Intermolecular interactions and the distribution of these interactions in all of these crystals were calculated by Hirshfeld surface analysis using Crystal Explorer 17.5 software. The emission spectrum of these compounds was recorded and the obtained results showed that the intensity of peaks has differences and the emission spectrum of the complexes changes by changing the lanthanide ions.

Nonplanar Aromaticity of Dinuclear Rare-Earth Metallacycles.

While the concept of metalla-aromaticity has well been extended to transition organometallic compounds in diverse geometries, aromatic rare-earth organometallic complexes are rare due to the special (n - 1)d0 configuration and high-lying (n - 1)d orbitals of rare-earth centers. In particular, nonplanar cases of rare-earth complexes have not been reported so far. Here, we disclose the nonplanar aromaticity of dinuclear scandium and samarium metallacycles characterized by various aromaticity indices (nucleus-independent chemical shift, isochemical shielding surface, anisotropy of induced current density, and isomerization stabilization energy). Bonding analyses (Kohn-Sham molecular orbital, adaptive natural density partitioning, multicenter bond indices, and principal interacting orbital) reveal that three delocalized π orbitals, predominantly contributed by the 2-butene tetraanion ligand, result in the formation of six-electron conjugated systems. Guided by these findings, we predicted that the lutetium and gadolinium analogues of dinuclear rare-earth metallacycles should be aromatic, which have been verified by the successful synthesis of real molecules. This work extends the concept of nonplanar aromaticity to the field of rare-earth metallacycles and illuminates the path for designing and synthesizing various rare-earth metalla-aromatics.

Temperature Induced Reversible Switching of the Magnetic Anisotropy in a Neodymium Complex Adsorbed on Graphite.

Controlling the magnetic anisotropy of molecular layers assembled on a surface is one of the challenges that needs to be addressed to create the next-generation spintronic devices. Recently, metal complexes that show a reversible solid-state switch of their magnetic anisotropy in response to physical stimuli, such as temperature and magnetic field, have been discovered. The complex Nd(trensal) (H3trensal=2,2',2''-tris(salicylideneimino)triethylamine) is predicted to exhibit such property. An ultra-thin film of Nd(trensal) is deposited on highly ordered pyrolytic graphite as a proof-of-concept system to show that this property can be retained at the nanoscale on a layered material. By combining single crystal magnetometric measurements and synchrotron X-ray-based absorption techniques, supported by multiplet ligand field simulations based on the trigonal crystal field surrounding the lanthanide centre, it is demonstrated that changing the temperature reverses the magnetic anisotropy of an ordered film of Nd(trensal), thus opening significant perspectives for the realization of a novel family of temperature-controlled molecular spintronic devices.

Charge compensation improves energy transfer to realize anti-thermal-quenching and enhances the CaMoO4: Sm3+ phosphors optical temperature measurement sensitivity base on the FIR model

Luminescent materials are the main focus of non-contact thermometers due to their high detection sensitivity, non-invasiveness, quick reaction, exceptional stability. It is still difficult to design high sensitivity optical temperature sensors using fluorescence intensity ratio technology. This article increases fluorescence intensity ratio value and obtains high sensitivity temperature sensitive phosphors by utilizing the anti-thermal-quenching effect of rare earth luminous centers. Sm3+ and alkali metal co-doped CaMoO4 phosphors have been prepared by high-temperature solid-state method. Rietveld refinement results showed that the co-doping of Sm3+ and K+ can significantly improve the energy transfer from the host to Sm3+ and significantly increase the luminous intensity of Sm3+. We found that co-doping of Sm3+ and K+ not only effectively enhanced the luminescence intensity, but also regulated the lifetime of this phosphors. When K+ is introduced into the CaMoO4: 0.02Sm3+, the τ value decreased from 4.12 to 3.54 ms, which proves to be effective in light-emitting diode. The optical temperature measurement of CaMoO4: 0.001Sm3+, 0.001 K+ was studied using fluorescence intensity ratio technology. The maximum SaMAX and SrMAX values are 0.27 K−1 at 483 K and 2.25 % K−1 at 363 K, respectively. Moreover, the CaMoO4: 0.02Sm3+, 0.02 K+ also has a certain absorption capacity in visible optical drive, which proved by ultraviolet visible diffused reflectance spectra. The electronic density of states of phosphors are drawn via first-principles to understand the effect of Sm3+ and alkali metals co-doped on luminescence. The above results demonstrate that the Sm3+ and K+ co-doping CaMoO4 might be an attractive material for the application of temperature measurement and light-emitting diode.

An Innovative SbIII-WVI-Cotemplated Antimonotungstate with Potential in Sensing Paroxetine Electrochemically.

Advances in polyoxometalate (POM) self-assembly chemistry are always accompanied by new developments in molecular blocks. The exploration and discovery of uncommon building blocks offer great possibilities for generating unprecedented POM clusters. An intriguing SbIII-WVI-cotemplated antimonotungstate [H2N(CH3)2]11Na[SbW9O33]Er2(H2O)2Sb2[SbWVIW15O57]·22H2O (1) was synthesized, which comprises a classical trivacant Keggin [SbW9O33]9- ({SbW9}) fragment and an unclassical lacunary Dawson-like [SbWVIW15O57]15- ({SbWVIW15}) subunit. Notably, the Dawson-like {SbWVIW15} subunit is the first example of a [SbO3]3- and [WVIO6]6- mixed-heteroatom-directing POM segment. Hexacoordinated [WVIO6]6- can not only serve as the heteroatom function but its additional oxygen sites can also link to lanthanide, main-group metal, and transition-metal centers to form the innovative structure. {SbWVIW15} and {SbW9} subunits are joined by the heterometallic [Er2(H2O)2Sb2O17]22- cluster to give rise to an asymmetric sandwich-type architecture. To further realize its potential application in electrochemical sensing, a conductive 1@rGO composite was obtained by the electrochemical deposition of 1 with graphene oxide (GO). Using a 1@rGO-modified glassy carbon electrode as the working electrode, an electrochemical biosensor for detecting the antidepressant drug paroxetine (PRX) was successfully constructed. This work can provide a viable strategy for synthesizing mixed-heteroatom-directing POMs and demonstrates the application of POM-based materials for the electrochemical detection of drug molecules.

Aluminium 8-Hydroxyquinolinate N-Oxide as a Precursor to Heterometallic Aluminium-Lanthanide Complexes.

A reaction in anhydrous toluene between the formally unsaturated fragment [Ln(hfac)3] (Ln3+ = Eu3+, Gd3+ and Er3+; Hhfac = hexafluoroacetylacetone) and [Al(qNO)3] (HqNO = 8-hydroxyquinoline N-oxide), here prepared for the first time from [Al(OtBu)3] and HqNO, affords the dinuclear heterometallic compounds [Ln(hfac)3Al(qNO)3] (Ln3+ = Eu3+, Gd3+ and Er3+) in high yields. The molecular structures of these new compounds revealed a dinuclear species with three phenolic oxygen atoms bridging the two metal atoms. While the europium and gadolinium complexes show the coordination number (CN) 9 for the lanthanide centre, in the complex featuring the smaller erbium ion, only two oxygens bridge the two metal atoms for a resulting CN of 8. The reaction of [Eu(hfac)3] with [Alq3] (Hq = 8-hydroxyquinoline) in the same conditions yields a heterometallic product of composition [Eu(hfac)3Alq3]. A recrystallization attempt from hot heptane in air produced single crystals of two different morphologies and compositions: [Eu2(hfac)6Al2q4(OH)2] and [Eu2(hfac)6(µ-Hq)2]. The latter compound can be directly prepared from [Eu(hfac)3] and Hq at room temperature. Quantum mechanical calculations confirm (i) the higher stability of [Eu(hfac)3Al(qNO)3] vs. the corresponding [Eu(hfac)3Alq3] and (ii) the preference of the Er complexes for the CN 8, justifying the different behaviour in terms of the Lewis acidity of the metal centre.

A route for determining absorption and emission cross-sections of rare-earth luminescence centers based on McCumber theory and Einstein coefficients

McCumber theory describes the relationship between the absorption cross-section and the emission cross-section of ionic luminescence centers. This theory is frequently used for determining absorption and emission cross-sections.

Energy exchange between Nd3+ and Er3+ centers within molecular complexes.

Developing controlled and reproducible molecular assemblies incorporating lanthanide centers is a crucial step for driving forward up- and down-conversion processes. This challenge calls for the development of strategies to facilitate the efficient in situ segregation of different Ln metal ions into distinct positions within the molecule. The unique family of pure [LnLn'Ln] heterometallic coordination compounds previously developed by us represents an ideal platform for studying the desired Ln-to-Ln' energy transfer (ET). In this context, we report here the new pure one-step synthetically produced [ErNdEr] (3) complex, which allows for the first time at the molecular level to study the mechanisms behind Nd-to-Er energy transfer. To further assess the photophysical properties of this complex, the analogous [LuNdLu] (1) and [ErLaEr] (2) complexes have also been prepared and photophysically studied. Efficient sensitization via the two β-diketones employed as main ligands was probed for both Nd3+ and Er3+ ions, resulting in highly resolved emission spectra and sufficiently long excited state lifetimes, which allowed further assessment of the Ln-to-Ln' ET. This intermetallic transfer was first detected by comparing the emission spectra of iso-absorbant solutions and demonstrated by comparing the lifetime values with or without the lanthanide quencher (Er3+), as well as with a deep analysis of the excitation spectrum of the three complexes. Thus, a very unique phenomenon was discovered, consisting of a mutual Nd-to-Er and Er-to-Nd ET with no net increase of brightness by any metal; while Nd3+ transfers the energy received from the antenna to Er3+, the sensitization of the latter results in back-transfer to Nd3+ into a non-emissive, thus silent, state.

Enhancing the magnetic properties of Dy(III) single-molecule magnets in octahedral coordination symmetry by tuning the equatorial ligands.

Conventionally, octahedral (Oh) coordination symmetry of lanthanide centers is not ideal for constructing high-performance single-molecule magnets (SMMs). However, introducing a strong ligand field in the axial direction to increase crystal field splitting can potentially overcome this limitation. Herein, we successfully obtained two dysprosium(III) single-molecule magnets, [Dy(OCtBu3)X2(py)3] (X = Cl (1), I (2), py = pyridine), in Oh coordination symmetry. The two complexes differ only in the coordinating anions on the equatorial plane, yet their magnetic performances are distinctly different. When chloride is replaced by a weaker donor iodide, the energy barrier is dramatically improved from 29 cm-1 (1) to 860 cm-1 (2), highlighting the importance of weakening the transverse ligand field and maximizing the axial ligand field for high-performance SMMs.

Sp2–sp cross-carbanion coupling at a rare-earth center leading to the formation of carbon–carbon double bonds

The reaction of rare-earth azametallacyclopentadienes with terminal alkynes provides rare-earth metallacycles with cumulated double bonds in three steps: alkynyl C–H bond activation, sp2–sp cross-carbanion coupling and subsequent isomerization.

Two-Electron Oxidations at a Single Cerium Center.

Two-electron oxidations are ubiquitous and play a key role in the synthesis and catalysis. For transition metals and actinides, two-electron oxidation often takes place at a single-metal site. However, redox reactions at rare-earth metals have been limited to one-electron processes due to the lack of accessible oxidation states. Despite recent advancements in nontraditional oxidation state chemistry, the low stability of low-valent compounds and large disparity among different oxidation states prevented the implementation of two-electron processes at a single rare-earth metal center. Here we report two-electron oxidations at a cerium(II) center to yield cerium(IV) terminal oxo and imido complexes. A series of cerium(II-IV) complexes supported by a tripodal tris(amido)arene ligand were synthesized and characterized. Experimental and theoretical studies revealed that the cerium(II) complex is best described as a 4f2 ion stabilized by δ-backdonation to the anchoring arene, while the cerium(IV) oxo and imido complexes exhibit multiple bonding characters. The accomplishment of two-electron oxidations at a single cerium center brings a new facet to molecular rare-earth metal chemistry.