Axial Elongation of Mononuclear Lanthanide Metallocenophanes: Magnetic Properties of Dysprosium‐ and Terbium‐[1]Ruthenocenophane Complexes

We report the first f‐block‐ruthenocenophane complexes 1 (Dy) and 2 (Tb) and provide a comparative discussion of their magnetic structure with respect to earlier reported ferrocenophane analogues. While axial elongation of the rare trigonal‐prismatic geometry stabilizes the magnetic ground state in the case of Dy³⁺ and results in a larger barrier to magnetization reversal (U), a decrease in U is observed for the case of Tb³⁺.     

Magnetoelectric compounds with two sets of magnetic sublattices: UCrO4 and NdCrTiO5

Using magnetic and magnetoelectric (ME) powder susceptibility measurements, the low temperature magnetic properties of antiferromagnetic UCrO₄ and NdCrTiO₅ have been studied. Their Néel temperatures T_N are 44.5 and 20.5°K, respectively, the Cr³⁺ spin systems of both materials ordering cooperatively at T_N. Below T_N, the U⁵⁺ and Nd³⁺ moments are polarized due to their exchange interaction with the ordered Cr³⁺ spins. It is argued that, for both compounds, each of the two spin systems contributes to the ME susceptibilities. They are thus the first known ME materials possessing two distinct magnetic sublattices. The effective magnetic moments calculated from the magnetic susceptibilities are in good agreement with those previously reported by neutron diffraction studies.     

Combined DFT and wave function theory approach to excited states of lanthanide luminescent materials: A case study of LaF3:Ce3+

Lanthanide luminescent materials play key roles in modern society, but their first-principles treatment remains a great challenge due to complex manifold of electronic excited states and the difficulty in performing excited state structural relaxations that is necessary to model luminescent properties. Herein, we propose a practical approach that combines embedded cluster model (ECM) based multi-configurational wave function theory (WFT) and occupancy constrained density-functional theory plus the Hubbard U correction (OC-DFT + U) to treat lanthanide doped luminescent materials, using LaF₃:Ce³⁺, a typical scintillator with low symmetry, as a case study. We show that the combined approach yields accurate absorption energies with an error on the order of 200 cm⁻¹, but the emission energies are significantly underestimated, the origin of which is further clarified by vibrationally resolved absorption and emission spectra calculation. This work demonstrates the possibility of combining ECM-based wave function theory and periodic DFT into a comprehensive computational scheme for lanthanide luminescent materials and highlights the limitations of the current implementation of OC-DFT + U for excited state structural optimization.     

Magnetic studies on ScyU1−yO2+x solid solutions

Magnetic susceptibilities of Sc_yU_1−yO_2+x solid solutions have been measured from 2.7 K to room temperature. The magnetic moment and Weiss constant have been determined in the temperature range in which the Curie-Weiss law holds. For the solid solutions showing antiferromagnetic transition, the Néel temperature has also been determined. The substitution of Sc³⁺ for U⁴⁺ was found to effect not only magnetic dilution of UO₂, but also oxidation of U⁴⁺ to U⁵⁺. Excess oxygen ions which entered the interstitial sites, weakened the antiferromagnetic interaction between uranium ions and oxidized U⁴⁺ to U⁵⁺. The effect of oxygen vacancies on the antiferromagnetic interaction was small in the concentration range of this experiment (0.8 a/o).     

Expanding the Chemistry of Molecular U2+ Complexes: Synthesis,Characterization, and Reactivity of the {[C5H3(SiMe3)2]3U}− Anion

The synthesis of new molecular complexes of U²⁺ has been pursued to make comparisons in structure, physical properties, and reactivity with the first U²⁺ complex, [K(2.2.2‐cryptand)][Cp′₃U], 1 (Cp′=C₅H₄SiMe₃). Reduction of Cp′′₃U [Cp′′=C₅H₃(SiMe₃)₂] with KC₈ in the presence of 2.2.2‐cryptand or 18‐crown‐6 generates [K(2.2.2‐cryptand)][Cp′′₃U], 2‐K(crypt) , or [K(18‐crown‐6)(THF)₂][Cp′′₃U], 2‐K(18c6) , respectively. The UV/Vis spectra of 2‐K and 1 are similar, and they are much more intense than those of U³⁺ analogues. Variable temperature magnetic susceptibility data for 1 and 2‐K(crypt) reveal lower room temperature χ_MT values relative to the experimental values for the 5f³ U³⁺ precursors. Stability studies monitored by UV/Vis spectroscopy show that 2‐K(crypt) and 2‐K(18c6) have t_1/2 values of 20 and 15 h at room temperature, respectively, vs. 1.5 h for 1 . Complex 2‐K(18c6) reacts with H₂ or PhSiH₃ to form the uranium hydride, [K(18‐crown‐6)(THF)₂][Cp′′₃UH], 3 . Complexes 1 and 2‐K(18c6) both reduce cyclooctatetraene to form uranocene, (C₈H₈)₂U, as well as the U³⁺ byproducts [K(2.2.2‐cryptand)][Cp′₄U], 4 , and Cp′′₃U, respectively.     

Uranium's Valency in U3S5

U₃S₅ has been prepared by chemical transport reaction and investigated using X-ray powder diffraction, FTIR spectroscopy, electrical resistivity measurements, and X-ray photoelectron spectroscopy. U₃S₅ is a semiconductor with a thermal band gap E_g=78.1(4) meV (298 K<T<50 K), which closes gradually to 3.4(4) meV for T<25 K. Photoelectron spectroscopy on single crystals of U₃S₅ and β-US₂ suggest a mixed valency of uranium in U₃S₅. Physical and structural data are consistent with a mixed-valent model (U³⁺)₂U⁴⁺ (S²⁻)₅. A brief survey of literature data on crystal structure and physical properties of uranium sulfides and selenides is given.     

Lanthanide‐Based Layer‐Type Two‐Dimensional Coordination Polymers Featuring Slow Magnetic Relaxation,Magnetocaloric Effect and Proton Conductivity

Three lanthanide‐based two‐dimensional (2D) coordination polymers (CPs), [Ln(L)(H₂O)₂]_n, {H₃L=(HO)₂P(O)CH₂CO₂H; Ln=Dy³⁺ (CP 1 ), Er³⁺ (CP 2 )} and [{Gd₂(L)₂(H₂O)₃}^.H₂O]_n, (CP 3 ) were hydrothermally synthesized using phosphonoacetic acid as a linker. Structural features revealed that the dinuclear Ln³⁺ nodes were present in the 2D sheet of CP 1 and CP 2 while in the case of CP 3 , nodes were further connected to each other forming a chain‐type arrangement throughout the network. The magnetic studies show field‐induced slow magnetic relaxation property in CP 1 and CP 2 with U_eff values of 72 K (relaxation time, τ₀=3.05×10^?7 s) and 38.42 K (relaxation time, τ₀=4.60×10^?8 s) respectively. Ab‐initio calculations suggest that the g tensor of Kramers doublet of the lanthanide ion (Dy³⁺ and Er³⁺) is strongly axial in nature which reflects in the slow magnetic relaxation behavior of both CPs. CP 3 exhibits a significant magnetocaloric effect with ?ΔS_m=49.29 J kg^?1 K^?1, one of the highest value among the reported 2D CPs. Moreover, impedance analysis of all the CPs show high proton conductivity with values of 1.13×10^?6 S cm^?1, 2.73×10^?3 S cm^?1 and 2, 6.27×10^?6 S cm^?1 for CPs 1 – 3 , respectively, at high temperature (>75 °C) and maximum 95 % relative humidity (RH).     

Eigenstates and radiative transition probabilities for Tm3+ (4f12) in phosphate and tellurite glasses

Electronic wavefunctions of Tm³⁺ in intermediate coupling were obtained and used to calculate the U^(λ) matrix elements between all possible states of the 4f¹² configuration. The Judd-Ofelt intensity parameters Ω_λ obtained for Tm³⁺ in phosphate and tellurite glasses were used in conjunction with the U^(λ)'s to calculate the forced electric dipole line strengths. The total electric and magnetic transition probabilities are calculated. The entire theoretical spectrum involving the ground and excited levels (from 129 nm to 16447 nm) is given.     

Slow magnetic relaxation in a novel carboxylate/oxalate/hydroxyl bridged dysprosium layer

A new 2D dysprosium layer compound has been successfully synthesized from reaction with 2-(3-pyridyl) pyrimidine-4-carboxylic acid (H3-py-4-pmc), in which the Dy³⁺ ions reside in square antiprismatic coordination environments and are connected by carboxylate/oxalate/hydroxyl bridges. Magnetic studies reveal ferromagnetic interactions between Dy³⁺ ions, slow magnetic relaxation with an effective energy barrier U _eff of 186 K under zero dc field and pronounced hysteresis loops at low temperatures. Further dilution magnetic study suggests that the slow magnetic relaxation originates from the single-ion magnetic behavior of Dy³⁺ ion and that magnetic coupling suppresses the quantum tunneling of magnetization at low temperature. In addition, theoretical calculation indicates strong Ising anisotropy of the Dy³⁺ ion that is due to the strong interaction between Dy³⁺ ions and hydroxyl groups.     

[UIII{N(SiMe2tBu)2}3]: A Structurally Authenticated Trigonal Planar Actinide Complex

We report the synthesis and characterization of the uranium(III) triamide complex [U^III(N**)₃] [ 1 , N**=N(SiMe₂tBu)₂^?]. Surprisingly, complex 1 exhibits a trigonal planar geometry in the solid state, which is unprecedented for three‐coordinate actinide complexes that have exclusively adopted trigonal pyramidal geometries to date. The characterization data for [U^III(N**)₃] were compared with the prototypical trigonal pyramidal uranium(III) triamide complex [U^III(N“)₃] (N”=N(SiMe₃)₂^?), and taken together with theoretical calculations it was concluded that pyramidalization results in net stabilization for [U^III(N“)₃], but this can be overcome with very sterically demanding ligands, such as N**. The planarity of 1 leads to favorable magnetic dynamics, which may be considered in the future design of U^III single‐molecule magnets.     

Synthesis of Isomeric Tb3+-Phthalocyanine Double-Decker Complexes Depending on the Difference in the Direction of Coordination Plane and Their Magnetic Properties

A C_4h symmetrically substituted phthalocyanine, 1,8,15,22-tertrakis(2,4-dimethylpent-3-oxy)phthalocyanine (H₂TdMPPc), was used to synthesize Tb³⁺-phthalocyanine double-decker complexes ([Tb(TdMPPc)₂]s). Because H₂TdMPPc has C_4h symmetry, S,S, R,R, and meso isomers of [Tb(TdMPPc)₂] were obtained depending on the difference in the direction of the coordination plane of two C_4h-type phthalocyanines with respect to a central Tb³⁺ ion. We investigated the physical properties of these [Tb(TdMPPc)₂] isomers, including their single-ion magnetic properties, and found that the spin-reversal energy barrier (U_eff) of the meso isomer was apparently higher than that of the enantiomers. Detailed crystal structural analyses indicated that the meso isomer has a more symmetrical structure than do the enantiomers, thereby suggesting that the higher U_eff of the meso isomer originated from the more highly symmetrical structure.     

Divergent Stabilities of Tetravalent Cerium,Uranium, and Neptunium Imidophosphorane Complexes**

The study of the redox chemistry of mid-actinides (U−Pu) has historically relied on cerium as a model, due to the accessibility of trivalent and tetravalent oxidation states for these ions. Recently, dramatic shifts of lanthanide 4+/3+ non-aqueous redox couples have been established within a homoleptic imidophosphorane ligand framework. Herein we extend the chemistry of the imidophosphorane ligand (NPC=[N=P^tBu(pyrr)₂]⁻; pyrr=pyrrolidinyl) to tetrahomoleptic NPC complexes of neptunium and cerium ( 1-M , 2-M , M=Np, Ce) and present comparative structural, electrochemical, and theoretical studies of these complexes. Large cathodic shifts in the M^4+/3+ (M=Ce, U, Np) couples underpin the stabilization of higher metal oxidation states owing to the strongly donating nature of the NPC ligands, providing access to the U^5+/4+, U^6+/5+, and to an unprecedented, well-behaved Np^5+/4+ redox couple. The differences in the chemical redox properties of the U vs. Ce and Np complexes are rationalized based on their redox potentials, degree of structural rearrangement upon reduction/oxidation, relative molecular orbital energies, and orbital composition analyses employing density functional theory.     

Electrochemistry of uranium in LiF–BeF2 melt

A study of the electrochemistry of uranium in LiF–BeF₂ system important for molten salt reactor concept was conducted at W and Ni electrodes. Cyclic voltammetry and chronopotentiometry methods were used. Two-step reduction mechanism for U⁴⁺ ions involving one electron exchange in soluble/soluble U⁴⁺/U³⁺ system and three electron exchange in the second step were found on W electrode. Both processes were identified as reversible and diffusion-controlled. Based on voltammetric and chronopotentiometric measurements, the diffusion coefficient of U⁴⁺ ions at 813 K was calculated: D(U⁴⁺) = 1.26 × 10⁻⁶ cm² s⁻¹ and D(U⁴⁺) = 1.28 × 10⁻⁶ cm² s⁻¹, respectively. Formation of U–Ni alloys was observed on Ni electrode.     

The [U2F12]2− Anion of Sr[U2F12]

The D_2h‐symmetric dinuclear complex anion [U₂F₁₂]^2? of pastel green Sr[U₂F₁₂] shows a hitherto unknown structural feature: The coordination polyhedra around the U atoms are edge‐linked monocapped trigonal prisms, the U^V atoms are therefore seven‐coordinated. This leads to a U–U distance of 3.8913(6) Å. A weak U^V–U^V interaction is observed for the dinuclear [U₂F₁₂]^2? complex and described by the antiferromagnetic exchange J_exp of circa ?29.9 cm^?1. The crystalline compound can be easily prepared from SrF₂ and β‐UF₅ in anhydrous hydrogen fluoride (aHF) at room temperature. It was studied by means of single crystal X‐ray diffraction, IR, Raman and UV/VIS spectroscopy, magnetic measurements, and by molecular as well as by solid‐state quantum chemical calculations.     

Thermal Responsive Ion Selectivity of Uranyl Peroxide Nanocages: An Inorganic Mimic of K+ Ion Channels

An actinyl peroxide cage cluster, Li_48+mK₁₂(OH)_m[UO₂(O₂)(OH)]₆₀ (H₂O)_n (m≈20 and n≈310; U₆₀), discriminates precisely between Na⁺ and K⁺ ions when heated to certain temperatures, a most essential feature for K⁺ selective filters. The U₆₀ clusters demonstrate several other features in common with K⁺ ion channels, including passive transport of K⁺ ions, a high flux rate, and the dehydration of U₆₀ and K⁺ ions. These qualities make U₆₀ (a pure inorganic cluster) a promising ion channel mimic in an aqueous environment. Laser light scattering (LLS) and isothermal titration calorimetry (ITC) studies revealed that the tailorable ion selectivity of U₆₀ clusters is a result of the thermal responsiveness of the U₆₀ hydration shells.     

Electrochemiluminescence in the reduction of uranyl ions on platinum in sulfuric acid solutions

Electrochemiluminescence (ECL) accompanying the reduction of uranyl ions on a platinum cathode in sulfuric solutions in the presence of XeO₃ was observed and studied. At early stages of the electrolysis (at 0.34<φ<0.62 V), the chemiluminescence reaction U^V+XeO₃ contributes mainly to the luminescence intensity, whereas at φ<0.32 V, the contribution of the reaction U^IV+XeO₃ predominates. The transfer coefficient for the primary electrochemical stage, formation of U^V, was estimated: α=0.46−0.54. The high sensitivity of ECL to the state of the electrode surface is explained by the fact that the reduction of U^VI occurs on the most active sites only. the background chemiluminescence reactions, among which U^V+O₂ and U^V+H₂O₂ can be distinguished, were considered, and their contributions to ECL were determined. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1928–1934, October, 1999.     

Magnetic ordering and metal‐atom site preference in tetragonal CrMnAs: Electronic correlation effects

The electronic and magnetic structures of tetragonal, Cu₂Sb‐type CrMnAs were examined using density functional theory. To obtain reasonable agreement with reported atomic and low‐temperature magnetic ordering in this compound, the intra‐atomic electron–electron correlation in term of Hubbard U on Mn atoms are necessary. Using GGA + U, calculations identify four low‐energy antiferromagnetically ordered structures, all of which adopt a magnetic unit cell that contains the same direct Cr Cr and Cr Mn magnetic interaction, as well as the same indirect Mn⋅⋅⋅Mn magnetic interaction across the Cr planes. One of these low‐energy configurations corresponds to the reported case. Effective exchange parameters for metal–metal contacts obtained from SPRKKR calculations indicate both direct and indirect exchange couplings play important roles in tetragonal CrMnAs. © 2018 Wiley Periodicals, Inc.     

Localization of electrons and excitations

Electrons, electron holes, or excitations in finite or infinite ‘multimer systems’ may be localized or delocalized. In the theory of Hush, localization depends on the ratio Δ/λ (Δ/2 = coupling; λ = reorganization energy). The latter theory has been extended to the infinite system [S. Larsson, A. Klimkāns, Mol. Cryst. Liq. Cryst. 355 (2000) 217]. The metal/insulator transition often takes place abruptly as a function of Δ/λ. It is argued that localization in a system with un-filled bands cannot be determined on the basis of Mott–Hubbard U alone, but depends on the number of accessible valence states, reorganization energy λ and coupling Δ (=2t). In fact U = 0 does not necessarily imply delocalization. The analysis here shows that there are many different situations for an insulator to metal transition. Charge transfer in doped NiO is characterized by Ni²⁺ − Ni³⁺ exchange while charge transfer in pure NiO is characterized by a disproportionation 2Ni²⁺ → Ni⁺ + Ni³⁺. In spite of the great differences between these two cases, U has been applied without discrimination to both. The relevant localization parameters appear to be Δ and λ in the first case, with only two oxidation states, and U, Δ and λ in the second case with three oxidation states. The analysis is extended to insulator-metal transitions, giant magnetic resistance (GMR) and high T_c superconductivity (SC). λ and Δ can be determined quite accurately in quantum mechanical calculations involving only one and two monomers, respectively.     

Influence of the Coordinated Transition Metal Ion on Magnetic Relaxation of Lanthanide Based Complexes with Imino Nitroxide Biradical Ligands

In spite of achievement of a lot of Ln-radical SMMs, how to improve magnetic behavior of Ln-radical system remains challenging. Here, two series of Ln-radical complexes have successfully been built using an imino nitroxide biradical, namely, [Ln₂(hfac)₆(ImPhPyobis)₂] (Ln^III=Gd 1 , Tb 2 , Dy 3 ) and [Ln₂Cu₂(hfac)₁₀(ImPhPyobis)₂] (Ln^III=Gd 4 , Dy 5 ; hfac=hexafluoroacetylacetonate and ImPhPyobis=5-(4-oxypyridinium-1-yl)-1,3-bis(1’-oxyl-4’,4’,5’,5’-tetramethyl-4,5-hydro-1H-imidazol-2-yl)benzene). For these biradical-metal complexes, two imino nitroxide biradicals bind two Ln(III) ions via their oxygen atoms coming from 4-oxypyridinium units to produce a binuclear {Ln₂O₂} unit. Those imino nitroxide groups are free for complexes 1 – 3 , however one of imino nitroxide groups of the biradical is ligated to the copper(II) ion for complexes 4 and 5 . The distinct magnetic relaxation behaviors are observed for two Dy derivatives, as revealed by ac magnetic studies: complex 3 presents one magnetic process with the effective energy barrier(U_eff) of 74.0 K while complex 5 exhibits dual relaxation processes with U_eff values for the fast- and slow-relaxation being 20.2 K and 30.9 K, respectively, which implies that the second coordination sphere of Dy ion plays a critical role for magnetic relaxation.