Specific features of phase equilibriums in Ln–Ba–Fe–O systems

Formation of five-layered Ln_2–εBa_3+εFe₅O_15–δ phases [exhibiting nanoscale ordering with layer-by-layer location of the cations in the Ln–Ba–(Ln,Ba)–(Ln,Ba)–Ba–Ln perovskite-type structure] has occurred in the Ln–Ba–Fe–O (Ln = Y, Pr, Nd, Sm, Eu, and Gd) systems at 1100°С in air. Partial substitution of iron with cobalt (Ln_2–εBa_3+εFe_5–yCo_yO_15–δ, Ln = Nd, Sm, Eu) has stabilized formation of the ordered structure. The oxygen content in the complex oxides has been determined in air over a wide temperature range by means of high-temperature thermogravimetry and iodometric titration. The change in oxygen content with temperature for the phases with five-layered ordering was significantly smaller than for the disordered phases.     

A variety of new tri- and tetranuclear Mn–Ln and Fe–Ln (Ln = lanthanide) complexes

The use of carboxylates in the synthesis of 3d/4f clusters, with or without a second organic ligand, has afforded a series of tetranuclear M₂Gd₂ complexes (M = Fe or Mn), and two new trinuclear M₂Gd (M = Fe or Mn) molecular compounds. Only one of these, [Mn₂Gd₂O₂(O₂CBu^t)₈(HO₂CBu^t)₄] (1), does not contain a multidentate chelate ligand. Two other similar tetranuclear clusters were synthesized from the use of triethanolamine (teaH₃) and 1,1,1-tris(hydroxymethyl)ethane (thmeH₃). [Mn₂Gd₂(OH)₂(O₂CPh)₄(NO₃)₂(teaH)₂] (2) has very similar structure with 1, bearing a defective incomplete double-cubane core bridged by μ₃-O atoms, whereas in the core of [NHEt₃]₂[Fe₂Gd₂(O₂CPh)₄(thme)₂(NO₃)₄] (3) the thme³⁻ ligand caps the two incomplete cubane units, providing the triply-bridging alkoxides needed for bridging. Two new oxide-centered triangular clusters were synthesized bearing the Schiff-based chelate 2-{[2-(dimethylamino)ethyl]methylamino}ethanol (dmemH), namely [Fe₂GdO(O₂CBu^t)₂(dmem)₂(NO₃)₃] (4), and [Mn₂GdO(O₂CBu^t)₂(dmem)₂(NO₃)₃] (5). Magnetic susceptibility measurements and/or reduced magnetization studies established that complexes 1 and 3 have an S = 5 ground state, complex 2 has S = 4, and complexes 4 and 5 are S = 7/2 in their ground states. These complexes portray the feasibility of obtaining products bearing metal cores commonly found in homometallic clusters, even when these include metals with completely different coordination chemistry and electronic structure, such as lanthanides.     

Structural Order–Disorder Transitions in Ln2Ti2O7 (Ln = Lu,Gd)

The phase generation in the Lu(Gd)–Ti–O systems is studied at 20–1000° using a co-precipitation method. During a thermal treatment of co-precipitation products after a sublimation dehydration, for a composition with the Lu : Ti cation ratio of 1 : 1, an Lu₂Ti₂O₇ phase with a fluorite structure forms at 650°. At 730–750°C the phase undergoes a fluorite pyrochlore transition. Above 750°C its structure is that of disordered pyrochlore, in which antistructural defects occur in Lu and Ti positions (up to 18%). Above 900°C the structure of pyrochlore becomes ordered, and the number of defects in Lu and Ti positions decreases, which affects the temperature dependence of permittivity of Lu₂Ti₂O₇. In Gd–Ti–O system, Gd₂Ti₂O₇ is crystallized, which has a pyrochlore structure only at 740–900°. Electroconductivity and permittivity of Lu₂Ti₂O₇ and Gd₂Ti₂O₇ are measured.     

Synthesis,structure and magnetic properties of unsymmetrical dodecanuclear Mn–Ln clusters

Reaction of manganese acetate and lanthanide nitrates in the presence of excess of PhCOOH affords highly asymmetric dodecanuclear mixed-metal [Mn₁₀Ln₂(OH)(O)₈(PhCOOH)(PhCOO)₁₉] (Ln = Pr^III (1), Nd^III (2)) clusters. The similar reaction, but with only 2 equiv. of PhCOOH resulted in the compounds with higher nuclearity [Mn₁₁Eu₄(O)₈(OH)₈(PhCOO)₁₈(NO₃)₂(H₂O)₆]NO₃ · 4CH₃CN (3). Variable-temperature solid-state magnetic susceptibility of 1 and 2 in the temperature range 1.8–300 K were carried out, and for both complexes antiferromagnetic exchange interactions between the metal centers were observed, giving an estimated S = 17/2 ground state. AC magnetic susceptibility data have revealed out-of-phase signals, which suggest that these complexes exhibit a slow relaxation of magnetization as observed in single-molecule magnets.     

New luminescent heteronuclear Ln(III)–Bi(III) complexes (Ln = Nd,Eu, Tb,Yb) based on aminopolycarboxylic acids

New heteronuclear Ln(III)–Bi(III) complexes (Ln?=?Nd, Eu, Tb, Yb, Lu) with ethylenediamine-N,N,N′,N′-tetraacetic (H₄edta), trans-1,2-cyclohexane-diamine-N,N,N′,N′-tetraacetic (H₄cdta), diethylenetriamine-N,N,N′,N″,N″-pentaacetic (H₅dtpa), and triethylenetetraamine-N,N,N′,N″,N″′,N″′-hexaacetic (H₆ttha) acids have been synthesized with a different synthetic approach. Bi(III) is a sensitizer of the 4f-luminescence in visible and near IR region. Emission spectra of Eu(III)–Bi(III) complexes were studied and the asymmetry of Eu(III) coordination environment was estimated, in good agreement with molecular models. The complexes synthesized by self-assembly are characterized by higher values of the 4f-luminescence quantum yield than other Ln(III)–Bi(III) complexes.     

Structures and luminescent properties of two heterotrimetallic Ln(III)–Sr(II)–K(I) complexes

Eu(III)–Sr(II)–K(I) and Tb(III)–Sr(II)–K(I) heterotrimetallic metal-organic frameworks with 2,4,6-pyridinetricarboxylic acid have been synthesized under hydrothermal conditions. The complexes are isomorphic and both in triclinic space group P-1. The ligands bond with three metal ions with two coordination modes. One connects seven metal ions and the other connects eight metal ions. IR spectra, thermal analysis, and photoluminescent properties have been studied. The results display strong characteristic emissions of Eu(III) or Tb(III) ions with excitation of ultraviolet radiation.     

Structure and physical properties of ternary NaF–LiF–LnF3 (Ln = La,Nd) systems of eutectic compositions

Ternary NaF–LiF–LnF₃ (Ln = La, Nd) systems of eutectic compositions were studied by means of X-ray diffraction method in the solid and liquid states. It was found that the crystalline phases LiF, NaF and NaLnF₄ coexist in the solid state up to the melting temperatures. Above the melting point, a decrease in the nearest interatomic distances with a pronounced minimum has been observed, which correlates with the extreme behaviour of the temperature-dependent structure-sensitive physical properties of the investigated alloys.     

Hydrothermal Synthesis,Crystal Structures,and Fluorescence Properties of Ni(II)–Ln(III) Complexes (Ln = Sm,Pr, Eu)

Three novel 3d–4f heterometal complexes [Ln(NiL)₃(Btca)(NO₃)] · xH₂O (Ln = Sm(III) (I), Pr(III) (II), Eu(III) (III) (H₂L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H₂Btca = benzotriazole-5-carboxylic acid) were solvothermally synthesized and characterized by singlecrystal X-ray diffraction (CIF files CCDC nos. 1555557 (I), 1555555 (II), 1555556 (III)). They crystallized in the monoclinic space group P2₁/n for I (x = 1.5) and C2/c for (II) and (III) (x = 1), respectively. In these complexes, the central Ln(III) and external nickel ions are bridged by macrocyclic oxamide groups. The metal center of Ln(III) resides in a distorted bicapped square antiprism surrounding with six oxygen atoms of three oxamide groups, two oxygen atoms of Btca^2– ion and two oxygen atoms of NO₃^-. Furthermore, there are C–H···O and/or C–H···N hydrogen bond interactions among nitrate, benzotriazole-5-carboxylate, macrocyclic oxamide and water to form three-dimensional superamolecular architecture. The fluorescence properties of the compounds I and II are also discussed.     

1-D Ln–Ag (Ln = Eu; Tb) heterometallic coordination polymers with pyridine-2,6-dicarboxylate as the single ligand: Synthesis,crystal structures,and luminescence

Two new 4d–4f heterometallic coordination polymers [AgLn(pydc)₂(H₂O)₃] · x(H₂O) [Ln = Eu, x = 1.25 (1); Ln = Tb, x = 1.25 (2); pydc = 2,6-pyridinedicarboxylate] have been synthesized and characterized by elemental analysis, IR spectroscopy, and single crystal X-ray diffraction. Both structures display the same unusual 1-D heterometallic coordination polymer based on Ln building blocks and Ag ions. Thermal stabilities and luminescent properties of 1 and 2 are presented.     

Ln2Cl 7 − ions (Ln = La and Lu): Structures and thermodynamic stability

The equilibrium geometrical parameters and frequencies of the normal vibrations of Ln₂Cl ₇ ^? ions (Ln = La and Lu) and the enthalpies of the dissociation reactions Ln₂Cl ₇ ^? → Ln₂Cl₆ + Cl^? and Ln₂Cl ₇ ^? → LnCl₃ + LnCl ₄ ^? were calculated at the MP2 and MP4 levels (with regard to single, double, triple, and quadruple perturbations). The basis set superposition errors were eliminated by using the counterpoise approach. The potential energy surface of the Ln₂Cl ₇ ^? ions was found to reach a minimum for a configuration with three bridging and four terminal Cl atoms (symmetry C ₂). The terminal fragments LnCl₂ show almost free inherent rotation. The lanthanide compression of the interatomic Ln-Cl distances differed for the bridging and terminal Ln-Cl bonds. The calculated enthalpies of dissociation of the Ln₂Cl ₇ ^? ions were compared with data from high-temperature mass spectrometry.     

Synthesis and magnetic characterization of Ln(III)–Co(II) complexes with 1,10-phenanthroline ligands

Four heteronuclear complexes, [Ln₂Co₂L₁₀(H₂O)(phen)₂] · n(H₂O) (Ln = La 1, n = 2; Ln = Nd 2, Sm 3, Gd 4, n = 0; HL = α-methylacrylic acid, phen = 1,10-phenanthroline), have been synthesized and characterized by elemental analysis, IR and X-ray diffraction. The complexes with a discrete Co–Ln–Ln–Co tetranuclear molecule are isomorphous in the triclinic space group P 1 and Z = 1, in which all metal ions are bridged by bidentate α-methylacrylato groups. Magnetic measurements of 1, 2 and 3 show antiferromagnetic exchange interaction between paramagnetic centers.     

四方相LaVO_4：Ln（Ln=Nd/Er）近红外发光纳米材料的水热合成

本文通过EDTA辅助的水热法合成了四方相稀土矾酸盐一维纳米材料,并通过Nd3＋或Er3＋掺杂使其具有近红外发光性质.与利用柠檬酸根作为配体合成得到的单斜相纳米晶相比,四方相矾酸盐具有更高的发光强度.通过对反应条件的改变,分别考察了EDTA-稀土离子投料比和掺杂离子浓度对产物形貌及发光性质的影响,发现在纳米尺度下,稀土离子具有更高的猝灭浓度.     

The Ln–Cu(II)–Hpic–H2BDC system showing interesting production variety upon different reaction conditions: hydrothermal synthesis,structures, thermostability,and magnetism

Herein, we report research regarding the Ln–Cu(II)–Hpic–H₂BDC system, where Ln, Hpic, and H₂BDC are lanthanide ions, picolinic acid, and 1,2-benzenedicarboxylic acid, respectively. Under different reaction temperatures (160°C and 170°C), the self-assembly of Gd₂O₃, CuCl₂, Hpic, and H₂BDC in water at pH = 2 adjusted by HClO₄ generates two Ln-containing coordination compounds, GdCu(pic)(PhCOO)₄ (1) and Gd(pic)(BDC)(µ-H₂O)₂(H₂O) (2) (PhCOOH = benzenecarboxylic acid). Under the same reaction conditions, if Gd₂O₃ is replaced by Pr₃O₄, then polymer Pr₄(BDC)₆(µ-H₂O)₂ (3) is obtained. The structural features are 1-D tape or 2-D irregular (6, 3) net. We also explored their phase purity by X-ray diffraction analysis and evaluated their thermostability by thermogravimetric analysis studies.     

A new 3-D microporous Ln(III)–Cu(I) framework constructed by pyridine-3,5-dicarboxylate

A new 3-D lanthanide-transition metal coordination polymer [LaCu(PDC)₂H₂O] _n (1) was hydrothermally synthesized from pyridine-3,5-dicarboxylic acid (H₂PDC) and characterized by single-crystal X-ray diffraction, IR spectroscopy, and thermal gravimetric analysis (TGA). The microporous framework of 1 can be viewed as constructed by planar binuclear Cu₂(PDC)₄ building blocks and La(III) chains, a new structural motif in 3d-4f heterometallic coordination polymers. The sample exhibits strong blue emission in the solid state and retains its framework integrity up to ca 380°C.     

Luminescent sol–gel materials based on lanthanide aminopolycarboxylates (Ln = Nd, Eu, Tb, Yb)

Luminescent organic–inorganic hybrid materials containing immobilized lanthanide(III) complexes (Ln = Nd, Eu, Tb, Yb) with modified ethylenediaminetetraacetic and diethylenetriaminepentaacetic acid were synthesized by sol–gel method. Obtained hybrids exhibit 4f-luminescence in the visible (Eu(III) and Tb(III)) and IR-region (Nd(III) and Yb(III)). The influence of the hybrid matrix on the lanthanide luminescence was established and it was shown, that the location of resonance level of Eu(III) is optimal for efficient energy transfer from matrix, while in the case of Tb(III) energy transfer does not occur and Tb(III) is able to absorb energy only due to its own week f–f transitions. It was also established that the inorganic matrix leads to elimination of nonradiative energy losses and increase of 4f-luminescence lifetimes. Covalent binding of Ln(III) aminopolycarboxylates in the matrix allows to consider obtained materials as promising for creation of photo- and chemically-stable luminescent sensors.     

Syntheses,structures and magnetic properties of isonicotinate-bridged heterometallic Ln(III)–Cu(II) coordination polymers

The heterometallic Ln(III)–Cu(II) coordination polymers [CuLn₂(IN)₈(H₂O)₄] _n (IN?=?isonicotinate, Ln?=?Gd (1), Dy (2), Er(3)) have been synthesized by hydrothermal reactions and characterized by elemental analysis, IR and single crystal X-ray diffraction. The compounds are isomorphous and crystallize in monoclinic space group P2₁/c, adopting a one-dimensional chain structure with alternately arranged [Ln₂(IN)₆(H₂O)₄] and [Cu(IN)₂] building blocks bridged by isonicotinates. Temperature-dependent magnetic susceptibility for complex 1 was studied, and a very weak ferromagnetic interaction between metal ions was observed.     

Oxidation resistance of LnSiON powders (Ln=Y,Gd and La)

For application of LnSiON (Ln=Y, Gd and La) oxynitride materials, e.g. as host-lattices for lamp phosphors, oxidation resistance up to about 600 °C in air is a prerequisite. In this study we prepared LnSiON (Ln=Y, Gd and La) powders by solid state reaction and observed via TGA/DTA-experiments that most compounds are oxidation resistant up to 600 °C in air. The stability in air at high temperatures increases going from Ln₅(SiO₄)₃N, Ln₄Si₂O₇N₂, LnSiO₂N, Ln₂Si₃O₃N₄ to Ln₃Si₈O₄N₁₁. This is explained by an increasing cross-linking between the siliconoxygennitrogen tetrahedra in this sequence. For the lattices with less cross-linking between the siliconoxygennitrogen tetrahedra we observed that the oxidation resistance decreases slightly going from Y and Gd to La. For these lattices, also, an additional weight gain was observed during the oxidation reaction, which was higher than expected for complete oxidation. The additional weight gain was ascribed to an intermediate phase in which nitrogen retention takes place.     

NMR SPECTROSCOPIC STUDY OF HETERONUCLEAR Ln(III)–Cu(II) METALLAMACROCYCLIC COMPLEXES IN AN AQUEOUS SOLUTION

Journal of Structural Chemistry - Polynuclear metallamacrocyclic Ln(III)–Cu(II) complexes in aqueous solutions are analyzed by 1H NMR. A structural feature of Ln(III)–Cu(II) [15-MC-5]...     

Ln（Ⅲ）—Cu（Ⅱ）—Ln（Ⅲ）多核配合物的合成与表征

合成了３种新的异三核配合物，其组成为（Ｌｎ２（ｂＰｙ）４（Ｃｕ（ｏＰｂａ）（ＣｌＯ４）２）（ＣｌＯ４）２，其中ｏＰｂａ表示邻苯双（草胺酸根），ｂＰｙ表示２，２′－联吡啶Ｌｎ表示Ｐｒ，Ｓｍ，Ｅｕ通过元素分析，红外光谱，紫外光谱，差热－热重及洋电导分析等手段，对它们的配位方式和某些物理化学性质进行了研究。     

甘氨酸辅助水热合成不同形貌的CaF2:Ln3+(Ln=Eu,Tb)微米晶

以KBF4和K2SiF6作为氟源,采用简单的甘氨酸辅助水热法制得了一系列具有不同形貌的CaF2:Ln3+(Ln =Eu,Tb)微米晶,如立方体、空心多面体和空心球.由XRD、FTIR、SEM及PL对产物的纯度、晶相、形貌和荧光性质进行了表征.XRD结果显示所有产物均为结晶良好的立方相CaF2.SEM结果表明,在添加甘氨酸的情况下,由KBF4得到的产物为空心多面体结构,而由K2SiF6制得的产物是由许多纳米块自组装成的空心球.研究发现甘氨酸、氟源种类、时间等反应参数在不同形貌CaF2:Ln3+(Ln=Eu,Tb)的形成过程中发挥关键作用,并提出了可能的反应机理.