H2O‐Catalyzed Route to Early Lanthanide Tribromide THF and DME Solvates from Oxides

A convenient one‐pot synthetic protocol towards THF and DME solvates of lanthanum and other early lanthanide tribromides was developed using the water‐catalyzed reaction of lanthanide(III) oxides with highly reactive Me₃SiBr in situ formed from commercially available disilane Si₂Me₆ and Br₂. This practical route allows to obtain the target lanthanum tribromide solvates [LaBr₃(thf)₄] ( 1a ) and [LaBr₃(dme)₂]₂ ( 1b ) as well as analogous early lanthanide molecular tribromide solvates [NdBr₃(thf)₄] ( 2a ), [NdBr₃(dme)₂] ( 2b ), [SmBr₃(thf)₂] ( 3a ), and [SmBr₃(dme)₂] ( 3b ) difficult to prepare by other solution‐based procedures. The molecular structure of 1b· 2CH₂Cl₂ was determined by an XRD study.     

Real‐time Probing the Formation of [M(2,2‐bipyridine)2(NO3)3] (M = Ce,La, Tb) Complexes and Influence of Synthesis Parameters

Despite the strong technological importance of lanthanide complexes, their formation processes are rarely investigated. This work is dedicated to determining the influence of synthesis parameters on the formation of [Ce(bipy)₂(NO₃)₃] as well as Ce³⁺‐ and Tb³⁺‐substituted [La(bipy)₂(NO₃)₃] (bipy = 2,2′‐bipyridine) complexes. To this end, we performed in situ luminescence measurements, synchrotron‐based X‐ray diffraction (XRD) analysis, infrared spectroscopy (IR), and measured pH value and/or ion conductivity during their synthesis process under real reaction conditions. For the [Ce(bipy)₂(NO₃)₃] complex, the in situ luminescence measurements initially presented a broad emission band at 490 nm, assigned to the 5d→4f Ce³⁺ ions within the ethanolic solvation shell. Upon the addition of bipy, a red shift to 700 nm was observed. This shift was attributed to the changes in the environment of the Ce³⁺ ions, indicating their desolvation and incorporation into the [Ce(bipy)₂(NO₃)₃] complex. The induction time was reduced from 8 to 3.5 min, by increasing the reactant concentration by threefold. In contrast, [La(bipy)₂(NO₃)₃] crystallized within days instead of minutes, unless influenced by high Ce³⁺ and Tb³⁺ concentrations. Monitoring and controlling the influence of the reaction parameters on the structure of emissive complexes is important for the development of rational synthesis approaches and optimization of their structure‐related properties like luminescence.     

Coordination and extraction studies of an unexplored bi-functional ligand,carbamoyl methyl pyrazole (CMPz) with uranium(VI), lanthanum(III) and cerium(III) nitrates

The bi-functional carbamoyl methyl pyrazole ligands, C₅H₇N₂CH₂CONBu₂ (L₁), C₅H₇N₂CH₂CONⁱBu₂ (L₂), C₃H₃N₂CH₂CONBu₂ (L₃), C₃H₃N₂CH₂CONⁱBu₂ (L₄) and C₅H₇N₂CH₂CON(C₈H₁₇)₂ (L₅) were synthesized and characterized by spectroscopic and elemental analysis methods. The selected coordination chemistry of L₁ to L₄ with [UO₂(NO₃)₂ · 6H₂O], [La(NO₃)₃ · 6H₂O] and [Ce(NO₃)₃ · 6H₂O] has been evaluated. Structures for the compounds [UO₂(NO₃)₂ C₅H₇N₂CH₂CONBu₂] (6) [UO₂(NO₃)₂ C₅H₇N₂CH₂CONⁱBu₂] (7) and [Ce(NO₃)₃{C₃H₃N₂CH₂CONⁱBu₂}₂] (11) have been determined by single crystal X-ray diffraction methods. Preliminary extraction studies of the ligand L₅ with U(VI) and Pu(IV) in tracer level showed an appreciable extraction for U(VI) and Pu(IV) up to 10 M HNO₃ but not for Am(III). Thermal studies of the compounds 6 and 7 in air revealed that the ligands can be destroyed completely on incineration.     

Binäre Lanthan‐Stannide mit Sn:La‐Verhältnissen nahe 1:1 – Synthesen,Kristallstrukturen, Chemische Bindung

Four binary lanthanum stannides close to the 1:1 ratio of Sn:La were synthesized from mixtures of the elements. The structures of the compounds have been determined by means of single‐crystal X‐ray data. The low temperature (α) form of LaSn (CrB‐type, orthorhombic, space group Cmcm, a = 476.33(6), b = 1191.1(2), c = 440.89(6) pm, Z = 4, R1 = 0.0247), crystallizes with the CrB‐type. The structure exhibits planar tin zigzag chains with a Sn–Sn bond length of 299.1 pm. In contrast to the electron precise Zintl compounds of the alkaline earth elements, additional La–Sn bonding contributions become apparent from the results of band structure calculations. In the somewhat tin‐richer region, the new compound La₃Sn₄ (orthorhombic, space group Cmcm, a = 451.45(4), b = 1190.44(9), c = 1583.8(2) pm, Z = 4, R1 = 0.0674), crystallizing with the Er₃Ge₄ structure type, exhibits Sn₃ segments of the zigzag chains of α‐LaSn together with a further Sn atom in a square planar Sn coordination with increased Sn–Sn bond lengths. In the Lanthanum‐richer region, La₁₁Sn₁₀ (tetragonal, space group I4/mmm, a = 1208.98(5), c = 1816.60(9) pm, Z = 4, R1 = 0.0325) forms the undistorted tetragonal Ho₁₁Ge₁₀ structure type. Its structure, which contains isolated Sn atoms, [Sn₂] dumbbells and planar [Sn₄] rings is related to the high temperature (β) form of LaSn. The structure of β‐LaSn (space group Cmmm, a = 1766.97(6), b = 1768.28(5), c = 1194.32(3) pm, Z = 60, R1 = 0.0453), which forms a singular structure type, can be derived from that of La₁₁Sn₁₀ by the removal of thin slabs. Due to the different stacking of the remaining layers, planar [Sn₄] chain segments and linear [Sn–Sn–Sn] anions are formed as additional structural elements. The chemical bonding (Sn–Sn covalent bonding, Sn–La contributions) is discussed on the basis of the simple Zintl concept and the results of FP‐LAPW calculations (density of states, band structure, valence electron densities and electron localization function).     

Tris(Trifluoroacetylacetonato)(4,4′-bipyridyl-N,N′-dioxido)Lanthanum(III)∶ A One-dimensional Polynuclear Complex

A novel one-dimensional polynuclear complex, tris(trifluoroacetylacetonato)(4,4'-bipyridyl- N , N '-dioxido)lathanum(III), was synthesized and characterized by elemental analysis and IR spectroscopy. X-ray structure analysis revealed that the complex has an infinite one-dimensional polynuclear structure with the 4,4'-bipyridyl- N , N '-dioxide as a bridge. La(III) is coordinated to eight oxygen atoms, six from three trifluoroacetylacetonate anions and two from two 4,4'-bipyridyl- N , N '-dioxide molecules to form a slightly distorted square antiprismatic coordination polyhedron. The coordination moiety was linked through 4,4'-bipyridyl- N , N '-dioxide forming a one-dimensional chain.     

Effect of citric acid and starch as emulsifier on phase formation and crystallite size of lanthanum oxide nanoparticles

Lanthanum oxide nanoparticles were synthesized via thermal decomposition method of the lanthanum nitrate in the presence of citric acid or starch as emulsifier. The effects of emulsifier and calcination temperature were investigated on the phase transformation and particle size distribution of the products. La₂O₃ nanoparticles were synthesized by drying lanthanum precursor and emulsifier solution, followed by calcination process at 600 and 900°C, respectively. Products were characterized by Fourier Transform Infrared (FT‐IR) spectroscopy, X‐ray diffraction (XRD), thermal analysis (TG/DTA) and nitrogen adsorption method (porous characteristics). The morphology of the samples analyzed using scanning electron microscopy (SEM). Average crystallite size of the products was calculated by XRD data and average particle size was measured from the TEM micrographs. Lanthanum dioxycarbonate in different forms of the tetragonal and monoclinic is crystallized in the presence of citric acid and starch during the calcination at 600°C, respectively. The hexagonal structure, however, is detected as the only crystalline phase formed by calcination at 900°C.     

The energy transfer mechanism in Ce,Tb co-doped LaF3 nanoparticles

LaF₃ pure host, LaF₃:Ce, LaF₃:Tb as well as LaF₃:Ce,Tb phosphors were synthesized by the hydrothermal method. X-ray diffraction measurements were in good agreement with the standard data of LaF₃ from JCPDS card No. 32-0483 and indicated that the material was nanocrystalline with an average particle size of about 36 nm. Photoluminescence spectra of co-doped samples revealed that the Ce³⁺ emission was quenched while Tb³⁺ emission was enhanced, implying that energy was transferred from Ce³⁺ (the donor) to Tb³⁺ (the acceptor) in this system. The luminescence intensities and lifetimes of the donor for different concentrations of the acceptor were fitted to theoretical models in order to investigate the energy transfer mechanism. The quadrupole–quadrupole and exchange interaction mechanisms gave the best fit between the experimental data and the theoretical curves. The effective average Bohr radius from the fit to the exchange model is 0.095 nm. Since this is close to the ionic radii of the Ce³⁺ and Tb³⁺ ions, it suggests that the exchange interaction mechanism contributes to the energy transfer.     

COMPLEXES OF MOLYBDENUM(V) AND LANTHANUM(III) WITH 2′,2″′-(2,6-PYRIDINEDIYLDIETHYLIDENE)-DIOXAMOHYDRAZIDE (H2DAPSOX)

Abstract

In a template synthesis from ethanolic solution of MoOCl₃, 2,6-diacetylpyridine (dap), and semioxamazide (sox), in the molar ratio 1:1:2, a dimeric molybdenum(V) complex [Mo₂O₂(H₂dapsox)₂]Cl₆ · 4H₂O (where H₂dapsox = 2′,2″′-(2,6-pyridinediyldiethylidenedioxa-mohydrazide) was obtained. In a similar reaction, starting from La(NO₃)₃ · 6H₂O, the complex [La(H₂dapsox)(NO₃) _x ](NO₃)_3-x · 1/2EtOH (x = 1,2), having coordination number 9, was obtained. In the latter complex two NO₃ Groups were bidentately coordinated in the solid state, but only one in the solution.

Besides [Mo₂O₂(TPP)₂] (TPP = tetraphenylporphyrin), the molybdenum(V) complex [Mo₂O₂ (H₂dapsox)₂]Cl₆ · 4H₂O is the only other known example of a dimeric μ-oxodimolybdenum(V) species that is paramagnetic (μ = 0.95 BM). One of the Mo atoms has pentagonal bipyramidal coordination, and the other pentagonal pyramidal coordination. In aqueous solution a rare example of a pentagonal pyramidal ion [MoO(dapsox)]⁺ is presumably present. Solution EPR spectra (at 77K) cannot be related to either of the two known types of Mo(V) species based on the extent of g anisotropy. The substances also were characterized by IR and electronic spectroscopy, and by thermal analysis.     

The mean activity coefficients of LaCl3 in dilute aqueous solution at 298.15 K

The electromotive forces of a symmetrical concentration cell with transference, Ag; AgCl|LaCl₃ (m*):LaCl₃ (m)|AgCl; Ag, were measured over the concentration range from 8.762 × 10⁻⁴ mol kg⁻¹ to 6.788 × 10⁻² mol kg⁻¹ at 298.15 K to obtain the mean activity coefficients of LaCl₃. The mean activity coefficient for reference solution at 298.15 K and the ion size parameter for LaCl₃ in the extended Debye–Hückel equation are evaluated by using an approach extrapolating concentration to unlimited dilution. A modified Debye–Hückel equation with new parameters has been established for the studied concentration range. A comparison is done of the thermodynamic data of LaCl₃ that are determined by this experiment with those reported by previous literatures, and evaluated by some models.     

水杨酸镧的流变相合成、表征及掺杂Tb3+的水杨酸镧的发光性质

用流变相反应法合成了水杨酸镧和掺杂Tb3 的水杨酸镧 ,通过元素分析 ,TG ,DTA ,X射线粉末衍射及红外光谱分析确定了水杨酸镧的组成、晶体结构和羧酸根与金属离子的配位方式 ,测定了掺杂Tb3 的水杨酸镧的激发和发射光谱 ,并对其发光特性进行了讨论。X射线粉末衍射表明该化合物为具有层状结构的单斜晶系 ,晶胞参数为 :a =2 1 6 0 1 0 ,b =1 3 80 1 5 ,c =3 81 0 3 ,β=97 1 1° ,V =1 1 2 7 2 3 ,Z =2 ,ρcal =1 6 2 1g·cm-3 ,ρexp =1 6 5 3g·cm-3 。掺杂Tb3 的水杨酸镧固体样品在紫外光激发下可观测到很强的三价铽离子的绿色发光 ,其中5D4→ 7F5的跃迁发射最强。