Complexes of gadolinium and erbium iodides with carbamide: Synthesis and structures

The novel carbamide complexes of gadolinium and erbium iodides of the composition LnI₃4Ur·4H₂O (Ln = Gd, Er; Ur = carbamide) were synthesized and studied by X-ray diffraction and IR spectroscopy. The ligands are coordinated to the central Gd or Er atom through the O atoms of water or carbamide molecules. The coordination polylhedron of Ln atoms is a distorted square antiprism. The iodide ions are not coordinated and lie in the outer sphere.     

Complexes of lanthanum,gadolinium, and erbium iodides with acetamide: Synthesis and structure

New acetamide complexes of lanthanum, gadolinium, and erbium iodides of the composition LnI₃ · 4AA · 4H₂ O (Ln = La, Gd, Er; AA = CH₃CONH₂) are synthesized and studied. The synthesized complexes are characterized by the data of chemical analysis and IR spectroscopy and are studied by X-ray diffraction analysis. The coordination of the ligands (water and acetamide molecules) by the lanthanum, gadolinium, or erbium atom occurs through the oxygen atoms. The coordination polyhedron of the Ln atom is a distorted square antiprism. The iodide ions are not coordinated and exist in the external sphere.     

Different Types of Coordinated Urea Molecules in its Complexes with Rare‐Earth Iodides and Perchlorates

An earlier reported series of the [Ln(Ur)₄(H₂O)₄]I₃ (Ln = Y, La, Nd, Eu, Gd, Dy, Ho, Er; Ur = urea) complexes was completed with seven new compounds (Ln = Ce, Pr, Sm, Tb, Tm, Yb, Lu); one of them, [Ce(Ur)₄(H₂O)₄]I₃, was studied by X‐ray diffraction. The most striking feature of the [Ln(Ur)₄(H₂O)₄]I₃ structures is the presence of two types of coordinated urea molecules. There are two planar symmetric and two non‐planar asymmetric urea molecules. The Ln–O–C bond angles vary in the ranges 163.06–165.71° and 148.42–152.42° for symmetric and asymmetric urea ligands, respectively, correlating with the ionic mode of urea coordination. To elucidate the role of aqua ligands for the urea coordination mode, two water‐free perchlorate complexes, [La(Ur)₈](ClO₄)₃ · 2Ur and [La(Ur)₇(OClO₃)](ClO₄)₂ were synthesized and structurally characterized. In these complexes, all urea molecules are planar symmetric; however, both covalent and ionic types of urea coordination with the La–O–C bond angles varying in the 132.4–142.3° and 145.5–159.1° ranges, respectively can be observed.     

Structural features of thiocarbamide derivatives of some lanthanide iodides

Data on the synthesis, IR spectroscopy, and single crystal XRD are presented for thiocarbamide compounds of the composition [Ln(H₂O)₉]I₃·2CS(NH₂)₂, where Ln = Dy (I) and Yb (II). The structural features of [Ln(H₂O)₉]I₃·2CS(NH₂)₂ (Ln = Pr, Nd, Eu, Gd, Dy, Ho, Er, and Yb) are discussed. The compounds of thiocarbamide with Pr, Nd, Eu, Gd, and Dy iodides are found to form the first isostructural series characterized by a continuous network structure, while with Ho, Er, and Yb iodides the second isostructural series with a layered type structure is formed.     

单N-乙酸取代O2N2大环配体及其稀土配合物的合成与表征

Aseries of new rare earth complexes LnL(NO₃)₂·2H₂O(Ln=La,Pr,Nd,Sm,Eu,Gd,Dy,Yb;L=1,2-diaza-3,4: 9,10-dibenzo-5,8-dioxyacyclopentadecane-N-acetic ion) were prepared. The complexes were characterized by elemental analysis, ICPmethod, IRspectra, 1H NMRand Molar conductance. It was found that the ether oxygen, carboxy oxygen and nitrogen atoms of the ligand are coordinated to the metal ion, as well as a free nitrate and coordianted nitrate ion in the complex.     

Double sulphates of plutonium(III) and lanthanides with sodium

Sodium plutonium double sulphate monohydrate, NaPu(SO₄)₂ · H₂O and its lanthanide isomorphs NaLn(SO₄)₂ · H₂O (Ln ≡ Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb) were synthesized and characterised by chemical and X-ray diffraction methods. All these compounds belonged to the same structural family where the Pu³⁺ or Ln³⁺ ion is coordinated to nine oxygen atoms. The structure of NaPu(SO₄)₂ · H₂O was found in the present work to be isomorphous with NaCe(SO₄)₂ · H₂O reported in the literature. The unit cells of all the lanthanide compounds showed regular contraction with atomic number.     

Vibrational spectra of hydrated rare earth orthophosphates

Weinschenkite-type LnPO₄·2H₂O (Ln is Gd, Tb, Dy, Ho, Y, Er, Tm or Yb) and rhabdophane-type, LnPO₄·H₂O (Ln is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb or Dy) have been investigated by IR absorption spectroscopy (4000–400 cm⁻¹) and Raman scanning spectroscopy (1400–100 cm⁻¹).The IR spectra of weinschenkite-type LnPO₄·2H₂O (Ln is Gd→Yb) are characterized by a band at 750±6 cm⁻¹ and the occurrence of a doublet in the region of the HOH bending vibrations, the low-frequency component exceeding the first high-frequency component in intensity. This rather peculiar pattern has already been observed in other compounds of similar chemical composition and is interpreted as arising from the presence of water molecules coordinated to the same metal cation. The Raman and IR spectra of these compounds have been interpreted in a manner based on the known structure of CaSO₄·2H₂O, which is isostructural with the weinschenkite-type compounds.The Raman and IR spectra of rhabdophane-type LnPO₄·H₂O is analyzed on the basis of the knowledge of the space group of rare earth orthophosphates rhabdophane-type. Its relation with the spectra of rare earth orthophosphates weinschenkite-type is discussed.     

The syntheses and magnetic properties of a series of heterospin [LnIIICuII 4] pentanuclear complexes

Twelve oxamide-bridged Ln(III)–Cu(II) heteropentanuclear complexes Ln[Cu(PMoxd)]₄(ClO₄)₃ · 5H₂O (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, and PMoxd = the N,N′-Bi(α-pyridylmethyl)-oxamide dianion) and 12 oxamide-bridged Ln(III)–Cu(II) heteropentanuclear complexes with the formula of Ln[Cu(PEoxd)]₄(ClO₄)₃ · 5H₂O (PEoxd = the N,N′-Bi(α-pyridylethyl)-oxamide dianion) were synthesized and characterized. The magnetic properties of Gd[Cu(PMoxd)]₄(ClO₄)₃ · 5H₂O (7) and Gd[Cu(PEoxd)]₄(ClO₄)₃ · 2H₂O (19) show that there are ferromagnetic interactions between Gd(III) and Cu(II) in the complexes with J _Cu–Gd = 1.38 cm^?1 and J _Cu–Gd = 1.00 cm^?1, respectively. Fluorescent quenching phenomena for Eu[Cu(PMoxd)]₄(ClO₄)₃ · 5H₂O (6) and Tb[Cu(PMoxd)]₄(ClO₄)₃ · 5H₂O (8) were also observed.     

Application of rotate-bomb calorimeter for determining the standard molar enthalpy of formation of Ln(Pdc)3(Phen)

Thirteen solid ternary complexes Ln(Pdc)₃(Phen) (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu;) have been synthesized in absolute ethanol by rare-earth element chloride low hydrate reacting with the mixed ligands of ammonium pyrrolidinedithiocarbamate (APdc) and 1,10-phenanthroline · H₂O (o-Phen · H₂O) in the ordinary laboratory atmosphere without any cautions against moisture or air sensitivity. IR spectra of the complexes showed that the Ln³⁺ ion was coordinated with six sulfur atoms of three Pdc⁻ and two nitrogen atoms of o-Phen · H₂O. It was assumed that the coordination number of Ln³⁺ is eight. The constant-volume combustion energies of the complexes, Δ_c U, were determined by a precise rotate-bomb calorimeter at 298.15 K. Their standard molar enthalpies of combustion, Δ_c H _m ^o , and standard molar enthalpies of formation, Δ_f H _m ^o were calculated. The text was submitted by the authors in English.     

Complexes of erbium and lutetium bromides with carbamide: Synthesis and structures

The synthesis and data of the study of new complexes of erbium and lutetium bromides with carbamide, [Ln(Ur)₄(H₂O)₄]Br₃ (I and III) and [Ln(Ur)₆(H₂O)₂]Br₃ (II and IV) (Ln = Er and Lu), by IR spectroscopy and X-ray diffraction analysis are presented. For all four compounds, coordination with metal occurs through the oxygen atoms of the water and carbamide molecules. The coordination polyhedra of the Ln atoms are distorted square antiprisms. Coordination of four carbamide molecules does not change their planar structures. The bromide ions are not coordinated, existing in the external sphere. Many hydrogen bonds are observed in the structures of complexes of both types.     

Lanthanide perchlorate complexes of 4-cyano pyridine-N-oxide, 4-chloro 2-picoline-N-oxide and 4-dimethyl amino-2-picoline-N-oxide

Complexes of lanthanide perchlorates with 4-cyano pyridine-1-oxide, 4-chloro 2-picoline-1-oxide and 4-dimethyl-amino 2-picoline-1-oxide have been isolated for the first time and characterized by analysis, conductance, infrared, NMR and electronic spectra. The complexes of 4-cyano pyridine-1-oxides have the composition Ln(CyPO)₆(ClO₄)₃. 2H₂O (Ln=La, Sm, Dy and Ho); Ln(CyPO)₇ (ClO₄)₃. 2H₂O (Ln=Pr, Nd, Er and Yb); and Ln(CyPO)₅ (ClO₄)₃. 2H₂O (Ln=Gd and Tb). The complexes of 4-chloro 2-picoline-1-oxide analyse for the formulae Ln(CpicO)₆ (ClO₄)₃ (Ln=La, Pr, Nd and Ho); and Ln (CpicO)₅ (ClO₄)₃ (Ln=Er and Yb), and those of 4-dimethylamino 2-picoline-1-oxide for Ln(DMPicO)₆ (ClO₄)₃ (Ln=La and Nd); Ln(DMPicO)₇ (ClO₄)₃ (Ln=Gd, Er and Yb); and Ln(DMPicO)₈ (ClO₄)₃ (Ln=Dy and Ho).     

Thermal behaviour of hydrated lanthanide complexes with heptanedioic acid

The multi-step dehydration and decomposition of trivalent lanthanum and lanthanide heptanediate polyhydrates were investigated by means of thermal analysis completed with infrared study. Further more, X-ray diffraction data for investigated heptanediate complexes of general stoichiometry Ln₂(C₇H₁₀O₄)₃.nH₂O (wheren=16 in the case of La, Ce, Pr, Nd and Sm pimelates,n=8 for Eu, Gd, Tb, Dy, Er and Tm pimelates,n=12 for Ho, Yb and Lu pimelates) were also reported.

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Zusammenfassung Mittels TG, DTG, DTA wurde in Verbindung mit IR-Methoden der mehrstufige Dehydratations- und der Zersetzungsvorgang der Polyhydrate der PimelinsÄuresalze von dreiwertigem Lanthan und dreiwertigen Lanthanoiden untersucht. Röntgendiffraktionsdaten der untersuchten Heptandiat-Komplexe mit der allgemeinen Formel Ln₂(C₇H₁₀O₄)₃ nH₂O (mitn=16 für Ln=La, Ce, Pr, Nd und Sm,n=8 für Ln=Eu, Gd, Tb, Dy, Er und Tm sowien=12 für Ln=Ho, Yb und Lu) werden ebenfalls gegeben.

     

Heteroleptic polypyrazolylborate derivatives of the lanthanide ions. The synthesis of acetylacetonate derivatives and the molecular structures of [Ln{HB(C3N2H3)3}2{MeC(O)CHC(O)Me}] (Ln = Ce,Yb)

The air and moisture stable complexes [Ln{HB(C₃N₂H₃)₃}₂{MeC(O)CHC(O)Me}] (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Yb, Lu, Y), have been prepared and characterized. The molecular structures of the compounds with Ln = Ce and Yb reveal that a substantial distortion of the coordination geometry found for Ce³⁺ is necessary to allow the ligand set to accommodate the smaller Yb³⁺ ion.     

Magneto,spectral and thermal studies of lanthanide perchlorato complexes of 5,6-benzoquinoline

A new series of complexes of 5,6-benzoquinoline (Benzqn) with lanthanide perchlorates with the general composition Ln(ClO₄)₃·7Benzqn (Ln = La, Ce, Pr, Nd, Sm, Gd, Tb, Dy or Ho) were synthesised and characterised by elemental analysis, conductance, molecular weight and infrared spectra. The thermal behaviour of these complexes have also been studied.     

3－乙酰乙酰基－4－羟基香豆素希土配合物的合成和性质

本文报道了稀土与３－乙酰乙酰基－４－羟基香豆素配合物的合成，其化学组成为Ｌｎ（Ｈａａｃ）３．ｎＨ２Ｏ（Ｌｎ为Ｌａ，Ｐｒ，Ｎｄ，Ｇｄ，Ｄｙ，Ｅｒ，ｎ为１或２），基于Ｈ－ＮＭＲ，ＩＲ的结果，提出了稀土离子与配位体４位羟基氧与邻近羰基双齿配位结构，对Ｎｄ＾３＋及Ｅｒ＾３＋配合物的超灵敏吸收带的形状和吸收强度等也作了讨论。     

Syntheses and Crystal Structures of Mononuclear and Binuclear Lanthanide Halide Complexes with Diglyme

Two types of isostructural complexes of lanthanide chlorides with diglyme have been synthesized. These are mononuclear molecular complexes [LnCl₃(diglyme)(THF)] (Ln = Eu ( 1 ), Gd ( 2 ), Dy ( 3 ), Er ( 4 ), Yb ( 5 ); diglyme = diethylen glycol dimethyl ether) and binuclear molecular complexes [LnCl₃(diglyme)]₂ (Ln = Dy ( 3d ), Er ( 4d ), Yb ( 5d )). Complex 1 was obtained by the reaction of [EuCl₃(DME)₂] with diglyme in THF. The complexes 2 – 5 and 3d – 5d resulted from reactions of LnCl₃·6H₂O, (CH₃)₃SiCl and diglyme in THF. The mononuclear complexes 2 – 5 crystallized directly from the solutions where the reactions of lanthanide compounds with diglyme took place. Recrystallizations of the powder products of the same reactions from dichloromethane resulted in the binuclear complexes 3d – 5d . Reactions of lanthanide bromide hydrates, (CH₃)₃SiBr and diglyme in THF achieved mononuclear molecular complexes [LnBr₃(diglyme)(L)] (Ln = Gd, L = H₂O ( 6 ); Ln = Ho, L = THF ( 7 )). Crystals of 6 and 7 were grown by recrystallization from dichloromethane. The lanthanide atoms (Ln = Eu–Yb) are seven‐coordinated in a distorted pentagonal bipyramidal fashion in all reported complexes, 1 – 7 and 3d – 5d . Four oxygen atoms and three halide ions are coordinated to lanthanide atoms in 1 – 7 , [LnX₃(diglyme)(L)]. Four chloride ions, two bridging and two nonbridging, and three oxygen atoms are coordinated to lanthanide atoms in 3d – 5d , [LnCl₃(diglyme)]₂.     

Lanthanide chelates of fluorinated β-diketones. Part II magnetic moments and electronic spectra of lanthanide chelates of four fluorinated β-diketones and the crystal structure of [Er(m · MeC6H4CO=CHCOF3)3(H2O)2] · H2O

Summary Magnetic and spectral data are reported for the complexes Ln(RCO=CHCOCF₃)₃ ·nH ₂O (Ln=lanthanide; R=p BrC₆H₄,m-MeC₆H₄,o-MeC₆H₄, Bu-t; n=2 or 3). An x-ray crystal structure determination of Er(m-MeC₆H₄CO=CH-COCF₃)₃ · 3 H₂O showed that the complex is eight-coordinate with three bidentate -diketonato and two aquo ligands; the third water molecule is hydrogen-bonded to one of the coordinated water molecules. The configuration about the erbium atom approximates to a square antiprism. The magnetic moments of the samarium and europium chelates are temperature-dependent, whereas those of the other paramagnetic lanthanides obey the Curie-Weiss law. The visible spectra of the chelates of Pr, Nd, Sin, Eu, Tb, Dy, Ho, Er, and Tm display line-like absorption bands typical of lanthanide ions. Hypersensitive transitions were observed for Nd, Sm, Eu, Dy, Ho, and Er.Part I,Transition Met. Chem., 8, 298 (1983).     

Syntheses and Crystal Structures of Lanthanide Chloride Complexes with Diglyme

Reactions of [LnCl₃(DME)₂] (Ln = Nd, Sm, Ho, Lu; DME = dimethoxyethane) and diglyme (diglyme = diethylen glycol dimethyl ether) in THF resulted in polymeric [LnCl₃(diglyme)]_n (Ln = Nd ( 1 ), Sm ( 2 )) or mononuclear complexes [LnCl₃(diglyme)(THF)] (Ln = Ho ( 3 ), Lu ( 4 )). Neodymium and samarium atoms in 1 and 2 are eight‐coordinated by three oxygen atoms from diglyme, one terminal and four bridging chloride ions. Holmium and lutetium atoms in 3 and 4 are seven‐coordinated by three oxygen atoms from diglyme, three chloride ions and one oxygen atom from THF. [ErCl₃(diglyme)(H₂O)] ( 5 ) resulted from the reaction of ErCl₃·6H₂O, (CH₃)₃SiCl and diglyme in THF. The molecular structures of 3 , 4 and 5 are similar, with either a molecule of THF coordinated to the lanthanide atom in 3 and 4 or with a molecule of water coordinated in 5 .     

Preparation of photoluminescent compounds of Eu(III), Sm(III), and Dy(III) containing anions of tetrafluoroterephthalic acid

The Ln₂(H₂O)₄(L)₃·2H₂O and Ln₂(phen)₂(L)₃·2H₂O complexes [Ln = Eu(III), Sm(III), or Dy(III); H₂L = C₆F₄(COOH)₂, phen = 1,10-phenanthroline] have been prepared. Structures of the prepared compounds have been confirmed by X-ray diffraction and IR spectroscopy studies. The complexes of Eu(III) have exhibited red photoluminescence stronger than that of the complexes of Sm(III) and Dy(III).