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1.
The solvent extraction of lanthanides(III) (Ln=Er, Yb, Lu) by 1-phenyl-3-methyl-4-benzoylpyrazolone-5 (HL) in carbon tetrachloride from aqueous-methanol phase was investigated. The equilibrium constants for the extraction from aqueous –50% (v/v) methanol phase (K ex ), two-phase stability constants of the complexesLnL 3 ( 3 * ) and stability constants of complexesLnL 2+,LnL 2 + ,LnL 3 ( n ) (Ln=Yb, Lu) were calculated. It was confirmed that the addition of methanol to the aqueous phase causes a synergistic effect. The influence of methanol on the dissociation constant of HPMBP (K a ) and the distribution constant of HPMBP (p HL ) between carbon tetrachloride and water-methanol solutions was investigated.
Extraktion von Seltenerdmetall-Ionen mit 1-Phenyl-3-methyl-4-benzoyl-pyrazolon-5 (HPMBP), II. Extraktion von Er(III), Yb(III) und Lu(III) aus Wasser-Methanol-Lösungen
Zusammenfassung Die Extraktion von Lanthaniden (Ln=Er, Yb, Lu) mittels 1-Phenyl-3-methyl-4-benzoyl-pyrazolon-5 (HL) in Kohlenstofftetrachlorid aus Wasser-Methanol Phase wurde untersucht. Die Werte der Gleichgewichtskonstante für Extraktion aus Wasser –50% (v/v) Methanol-Phase (K ex ), der zweiphasigen Beständigkeitskonstante für die KomplexeLnL 3 ( 3 * ), sowie der Stabilitätskonstante des KomplexesLnL 2+,LnL 2 + undLnL 3 ( n ) (Ln=Yb, Lu), wurden berechnet. Es wurde festgestellt, daß die Zugabe von Methanol zur wäßrigen Phase einen synergistischen Effekt hat. Der Einfluß von Methanol auf die Dissoziationskonstante von HPMBP (K a ) und die Verteilungskonstante des HPMBP (p HL zwischen organischer und wäßrig-methanolischer Phase wurde untersucht.
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2.
Compounds ScL 2(NO3)3·2 H2O,LnL 2(NO3)3·H2O (Ln=Pr, Sm, Eu, Gd, Tb),LnL 2(NO3)3·3 H2O (Ln=Nd, Dy, Ho, Er),LnL 3(NO3)3 (Ln=Pr, Nd) andLnL 3(NO3)3· ·3 H2O (Ln=Sc, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were isolated. They were investigated by means of thermoanalysis, IR spectroscopy, X-ray diffraction and molar conductivity.

L=2,2-Bipyridin-N,N-dioxid=bpyO2=C10H8N2O2.  相似文献   

3.
Solid-state compounds of general formula LnL3⋅nH2O, where Ln represents heavier lanthanides and yttrium and L is 2-chlorobenzylidenepyruvate, have been synthesized. Chemical analysis, simultaneous thermogravimetry-differential analysis (TG-DTA), differential scanning calorimetry (DSC), X-ray powder diffractometry, elemental analysis and infrared spectroscopy have been employed to characterize and to study the thermal behaviour of these compounds in dynamic air atmosphere. On heating these compounds decompose in four (Gd, Tb, Ho to Lu, Y) or five (Eu, Dy) steps. They lose the hydration water in the first step and the thermal decomposition of the anhydrous compounds up to 1200°C occurs with the formation of the respective oxide, Tb4O7 and Ln2O3 (Ln=Eu, Gd, Dy to Lu and Y) as final residue. The dehydration enthalpies found for these compounds (Eu, to Lu and Y) were: 65.77, 55.63, 86.89, 121.65, 99.80, 109.59, 131.02, 119.78, 205.46 and 83.11 kJ mol-1, respectively.  相似文献   

4.
The formation ofPAN complexes in the systemsLn(III)—PAN—alcohol-water (where:Ln(III)=Ho, Lu and alcohol=ethanol,n-propanol,iso-propanol) was investigated by a spectrophotometric method. Equilibrium constants for the reactionLn 3+ + HLLnL 2+ + H+ (HL=PAN) and stability constants of complexesLnL 2+ were calculated.
Untersuchungen zur Komplexbildung von Ho(III) und Lu(III) mit 1-(2-Pyridylazo)-2-naphthol (PAN) in alkoholisch-;wä\rigen Lösungen
Zusammenfassung Die Bildung der Komplexe vonPAN in den SystemenLn(III)—PAN—Alkohol-Wasser (Ln(III)=Ho, Lu; Alkohol=Ethanol,n-Propanol,iso-Propanol) wurde mit einer spektrophotometrischen Methode untersucht. Die Gleichgewichtskonstanten der ReaktionenLn 3+ + HLLnL 2+ + H+ (HL==PAN) und die Stabilitätskonstanten der KomplexeLnL 2+ wurden berechnet.
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5.
The formation ofPAN complexes in the systems:Ln(III)—PAN—alcohol—water [whereLn(III) = Pr, Nd, Sm, Eu, Gd, Tb, alcohol - ethanol andLn(III) = Eu, alcohol =n-propanol, isopropanol] was investigated by a spectrophotometric method. Equilibrium constants for the reactionLn 3++HLLnL 2++H+ (HL =PAN) and stability constants of complexesLnL 2+ are reported.
Komplexbildung einiger Seltenerdmetalle mit 1-(2-Pyridylazo)-2-naphthol (PAN) in alkoholisch-wäßrigen Lösungen
Zusammenfassung Die Bildung der Komplexe vonPAN in den SystemenLn(III)—PAN—Alkohol—Wasser [Ln(III) = Pr, Nd, Sm, Eu, Gd, Tb, Alkohol = Ethanol undLn(III) = Eu, Alkohol =n-Propanol, Isopropanol] wurde mit einer spektrophotometrischen Methode untersucht. Die Gleichgewichtskonstanten der ReaktionenLn 3++HLLnL 2++H+ (HL =PAN) und die Stabilitätskonstanten der KomplexeLnL 2+ wurden berechnet.
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6.
The complexes of yttrium and heavy lanthanides with 3,4-dimethoxybenzoic acid of the formula: Ln(C9 H9 O4 )3 ×n H2 O, where Ln =Y(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III) and Lu(III), and n =4 for Tb(III), Dy(III), n =3 for Ho(III), and n =0 for Er(III), Tm(III), Yb(III), Lu(III) and Y(III) have been prepared and characterized by elemental analysis, IR spectroscopy, thermogravimetric and magnetic studies and X-ray diffraction measurements. The complexes have colours typical of Ln3+ ions (Ho - cream, Tb, Dy, Yb, Lu, Y - white, Er - salmon). The carboxylate group in these complexes is a symmetrical, bidentate, chelating ligand. They are crystalline compounds characterized by various symmetry. On heating in air to 1273 K the hydrated 3,4-dimethoxybenzoates decompose in two steps while those of anhydrous only in one stage. The tetrahydrates of Tb and Dy and trihydrate of Ho 3,4-dimethoxybenzoates are firstly dehydrated to form anhydrous salts that next are decomposed to the oxides of the respective metals. The complexes of Er, Tm, Yb, Lu and Y are directly decomposed to the oxides of the appropriate elements. The solubility in water at 293 K for yttrium and heavy lanthanides is in the order of 10-4 -10-3 mol dm-3 . The magnetic moments of the complexes were determined over the range 77–298 K. They obey the Curie-Weiss law. The values of μeff calculated for all compounds are close to those obtained for Ln3+ by Hund and van Vleck. The results show that there is no influence of the ligand field on 4f electrons of lanthanide ions in these polycrystalline compounds and 4f electrons do not take part in the formation of M-O bonding. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

7.
Compounds of the type CsLn(SO4)2, (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were prepared at 300°C. IR spectra were recorded in the range 4,000-250cm–1 and tentatively assigned. The number of observed bands exceeds the predicted number by site symmetry selection rules. Streching bands show bathochromic shifts whereas the deformations exibit hypsochromic shifts on going to heavier lanthanides. At the same time there is an increased splitting of these bands in the same direction. All these facts indicate an increased coupling in the layer structure which is in accordance with the lanthanide contraction.
N. Bukovec, P. Bukovec undJ. iftar, Vest. Slov. Kem. Drus.26, 103 (1979).  相似文献   

8.
The complexes of heavy lanthanides and yttrium with 2,3-dimethoxybenzoic acid of the formula: Ln(C9h9O4)3·nH2O, where Ln=Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), Lu(III), Y(III), and n=2 for Tb(III), Dy(III), Ho(III), Y(III), n=1 for Er(III), Tm(III), n=0 for Yb(III) and Lu(III) have been synthesized and characterized by elemental analysis, ir spectroscopy, thermogravimetric studies and x-ray diffraction measurements. The complexes have colours typical for Lnł3+ ions (Tb(III), Dy(III), Tm(III), Yb(III), Lu(III), Y(III) - white; Ho(III) - cream and Er(III) - salmon). the carboxylate groups in these complexes are a symmetrical, bidentate, chelating ligand or tridentate chelating-bridging. they are isostructural crystalline compounds characterized by low symmetry. On heating in air to 1273 k the 2,3-dimethoxybenzoates of heavy lanthanides and yttrium decompose in various ways. The complexes of Tb(III), Dy(III), Ho(III), Er(III), Tm(III) and Y(III) at first dehydrate to form anhydrous salts which next are decomposed to the oxides of the respective metals. 2,3-dimethoxybenzoates of Yb(III) and Lu(III) are directly decomposed to oxides. When heated in nitrogen the hydrates also dehydrate in one step to form the anhydrous complexes that next form the mixture of carbon and oxides of respective metals or their carbonates. The solubility of the yttrium and heavy lanthanide 2,3-dimethoxybenzoates in water at 293 k is of the order of 10-2 mol dm-3. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

9.
The efficiency of extraction of microquantities of Eu(III), Sm(III) and Gd(III) from water—50% (v/v) methanol phase or water—50% (v/v) ethanol phase withPAN solutions in CCl4 was examined. Separation factors for the following pairs of lanthanides(III) were determined: Eu-Sm, Eu-Gd, Sm-Gd, as well as Eu-Ln, Sm-Ln and Gd-Ln, where:Ln=Tb, Ho, or Lu; their changes with respect to the composition of the polar phase were also estimated.
Der Einfluß von Methanol und Ethanol auf die Effektivität der Extraktion der Lanthaniden mit Lösungen von 1-(2-pyridylazo)-2-naphthol (PAN) in Tetrachlorkohlenstoff
Zusammenfassung Die Effektivität der Extraktion von Mikromengen Eu(III), Sm(III) und Gd(III) aus der Wasser-Methanol- und Wasser-Ethanol-Phase (50 vol. %), mit Hilfe vonPAN-Lösungen in CCl4 wurde untersucht. Die Trennfaktoren für nachstehende Lanthaniden(III)-Paare: Eu-Sm, Eu-Gd, Sm-Gd und Eu-Ln, Sm-Ln, Gd-Ln(Ln=Tb, Ho oder Lu) wurden berechnet und ihre Änderungen in der Abhängigkeit von der polaren Phase geschätzt.
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10.
Zusammenfassung Substanzen der ZusammensetzungLnCl3·3H2 Box * (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Y) und LaBr3·3 H2 Box wurden isoliert und durch Thermoanalyse, IR-Absorptionsspektren und Röntgenstreuung charakterisiert.
Compounds of the rare earth elements with -benzoin oxime
Compounds of compositionLnCl3·3 H2 Box * (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Y) and LaBr3·3H2 Box were isolated and characterized by thermoanalysis, IR spectroscopy and X-ray diffraction.
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11.
Solid-state Ln(L)3 compounds, where Ln stands for trivalent Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y and L is 2-methoxybenzoate have been synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), X-ray powder diffractometry, infrared spectroscopy and complexometry were used to characterize and to study the thermal behaviour of these compounds. The results provided information on the composition, dehydration, coordination mode, structure, thermal behaviour and thermal decomposition.  相似文献   

12.
Compounds [Fe3Ln(tea)2(dpm)6] ( Fe3Ln ; Ln= Tb–Yb, H3tea=triethanolamine, Hdpm=dipivaloylmethane) were synthesized as lanthanide(III)‐centered variants of tetrairon(III) single‐molecule magnets (Fe4) and isolated in crystalline form. Compounds with Ln=Tb–Tm are isomorphous and show crystallographic threefold symmetry. The coordination environment of the rare earth, given by two tea3? ligands, can be described as a bicapped distorted trigonal prism with D3 symmetry. Magnetic measurements showed the presence of weak ferromagnetic Fe ??? Ln interactions for derivatives with Tb, Dy, Ho, and Er, and of weak antiferromagnetic or negligible coupling in complexes with Tm and Yb. Alternating current susceptibility measurements showed simple paramagnetic behavior down to 1.8 K and for frequencies reaching 10000 Hz, despite the easy‐axis magnetic anisotropy found in Fe3Dy , Fe3Er , and Fe3Tm by single‐crystal angle‐resolved magnetometry. Relativistic quantum chemistry calculations were performed on Fe3Ln (Ln=Tb–Tm): the ground J multiplet of Ln3+ ion is split by the crystal field to give a ground singlet state for Tb and Tm, and a doublet for Dy, Ho, and Er with a large admixture of mJ states. Gyromagnetic factors result in no predominance of gz component along the threefold axis, with comparable gx and gy values in all compounds. It follows that the environment provided by the tea3? ligands, though uniaxial, is unsuitable to promote slow magnetic relaxation in Fe3Ln species.  相似文献   

13.
Summary Complexes of heavy lanthanide(III) (Gd-Lu) and Y(III) with 4-chlorophthalic acid were prepared and their IR spectra, solubility in water at 295 K and thermal decomposition were investigated. When heated the complexes with general formula Ln2[ClC6H3(CO2)2]3·nH2O where n=6 for Tb, Dy(III), n=4 for Gd, Ho and Er(III), n=2 for Tm-Lu(III) and n=3 for Y(III) decompose to the oxides Ln2O3, Tb4O7 with intermediate formation of oxochlorides LnOCl.  相似文献   

14.
The complexes of yttrium and heavy lanthanides with 2,4-dimethoxybenzoic acid of the formula: Ln(C9H9O4)3×nH2O, where Ln=Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), Lu(III) and Y(III), n=2 for Tb(III), Dy(III), Ho(III), Er(III), Tm(III) and Y(III), and n=0 for Yb(III) and Lu(III), have been synthesized and characterized by elemental analysis, IR spectroscopy, themogravimetric studies, as well as X–ray and magnetic susceptibility measurements. The complexes have a colour typical of Ln 3+ salts (Tb, Dy, Tm, Yb, Lu, Y – white, Ho – cream, Er – pink). The carboxylate group in these complexes is a bidentate, chelating ligand. The compounds form crystals of various symmetry. 2,4-Dimethoxybenzoates of Yb(III) and Lu(III) are isostructural. 2,4-Dimethoxybenzoates of yttrium and heavy lanthanides decompose in various ways on heating in air to 1173 K. The hydrated complexes first lose water to form anhydrous salts and then decompose to the oxides of respective metals. The ytterbium and lutetium 2,4-dimethoxybenzoates decompose in one step to form Yb2O3 and Lu2O3. The solubilities of the 2,4-dimethoxybenzoates of yttrium and heavy lanthanides in water and ethanol at 293 K are of the order of: 10–3 and 10–3 –10–2 mol dm–3, respectively. The magnetic moments for the complexes were determined over the range of 77–298 K. They obey the Curie–Weiss law. The results show that there is no influence of the ligand field on the 4f electrons of lanthanide ions. This revised version was published online in August 2006 with corrections to the Cover Date.  相似文献   

15.
Neutral complexes of composition [LnL3Phen], where Ln = Tm, Dy, and Gd, were synthesized by the reaction of LnCl3 with heterocyclic diketone 1,3-bis(1,3-dimethyl-1H-pyrazol-4-yl)-1,3-propanedione (HL, 1) and 1,10-phenanthroline in an aqueous alcohol solution in the presence of NaOH. The composition of the complexes was proved by elemental analysis. Their optical and luminescence properties were studied.  相似文献   

16.
4,4-Dipyridyl and 2,2-dipyridyl complexes of rare-earth perchlorates of the formulaLn(4-dipy)8(ClO4)3HClO4 · 4H2O (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y, 4-dipy=4,4-dipyridyl) andLn(2-dipy)3(ClO4)3 · 6H2O (Ln=Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y, 2-dipy = 2,2-dipyridyl) have been synthesized. The IR spectra of these compounds and other physical properties are discussed.
4,4-Dipyridyl- und 2,2-Dipyridylkomplexe von Seltenerdmetallperchloraten
Zusammenfassung Es wurden 4,4-Dipyridylkomplexe des TypsLn(4-dipy)8(ClO4)3HClO4 · · 4 H2O mitLn=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y und 2,2-Dipyridylkomplexe des TypsLn(2-dipy)3(ClO4)3 · 6 H2O mitLn=Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu und Y dargestellt. Die IR-Spektren und andere physikalische Eigenschaften werden diskutiert.
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17.
Synthesis of lanthanide-containing (Ln = Eu, Tb, Nd, Gd) monomers based on unsaturated acids is described, namely, of LnL1 3 · nH2O (L1 are anions of acrylic and methacrylic acids) and Ln2L2 3 · nH2O (L2 are anions of maleic and fumaric acids); n = 0–3, 6. The compounds were characterized by elemental analysis, thermogravimetry, and IR and luminescence spectroscopy. Europium methacrylate Eu(Macr)3 was studied using X-ray diffraction analysis: rhombic system, a = 14.831(3) Å, b = 12.964(2) Å, c = 7.761(1) Å, space group Cmc21, V = 1483.5(4) Å3, (calcd) = 1.823 g/cm3. Infinite chains of Eu(Macr)3 molecules are directed along crystallographic axis c and are bound by van der Waals interactions. Radical polymerization of Eu(III) and Tb(III) acrylates and Eu(III) methacrylate yields lanthanide-containing polymers with a high content of Ln (40–50 mass %). Their spectral and luminescent properties are studied.  相似文献   

18.
The conditions of thermal decomposition of Tb(III), Dy, Ho, Er, Tm, Yb and Lu aconitates have been studied. On heating, the aconitates of heavy lanthanides lose crystallization water to yield anhydrous salts, which are then transformed into oxides. The aconitate of Tb(III) decomposes in two stages. First, the complex undergoes dehydration to form the anhydrous salt, which next decomposes directly to Tb4O7. The aconitates of Dy, Ho, Er, Tm, Yb and Lu decompose in three stages. On heating, the hydrated complexes lose crystallization water, yielding the anhydrous complexes; these subsequently decompose to Ln2O3 with intermediate formation of Ln2O2CO3.  相似文献   

19.
A family of 3d–4f aggregates have been reported through guiding the dual coordination modes of ligand anion (HL?) and in situ generated ancillary bridge driven self‐assembly coordination responses toward two different types of metal ions. Reactions of lanthanide(III) nitrate (Ln=Gd, Tb, Dy, Ho and Yb), nickel(II) acetate and phenol‐based ditopic ligand anion of 2‐[{(2‐hydroxypropyl)imino}methyl]‐6‐methoxyphenol (H2L) in MeCN‐MeOH (3 : 1) mixture and LiOH provided five new octanuclear Ni‐4f coordination aggregates from two Ni2Ln2 cubanes. Single‐crystal X‐ray diffraction analysis reveals that all the members of the family are isostructural, with the central core formed from the coupling of two distorted [Ni2Ln2O4] heterometallic cubanes [Ni2Ln2(HL)2(μ3‐OH)2(OH)(OAc)4]+ (Ln=Gd ( 1 ), Tb ( 2 ), Dy ( 3 ), Ho ( 4 ) and Yb ( 5 )). Higher coordination demand of 4f ions induced the coupling of the two cubes by (OH)(OAc)2 bridges. Variable temperature magnetic study reveals weak coupling between the Ni2+ and Ln3+ ions. For the Tb ( 2 ) and Dy ( 3 ) analogs, the compounds are SMMs without an applied dc field, whereas the Gd ( 1 ) analogue is not an SMM. The observation revealed thus that the anisotropy of the Ln3+ ions is central to display the SMM behavior within this structurally intriguing family of compounds.  相似文献   

20.
4,4-Dipyridyl complexes of rare-earth thiocyanates of the formulaLn(4-dipy)2(NCS)3·5H2O (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y, 4-dipy = 4,4-dipyridyl) have been synthesized. The IR spectra of these compounds and other physical properties are discussed. The thermal decomposition of some compounds (in the order Gd ÷ Lu) has been investigated.
4,4-Dipyridylkomplexe von Seltenerdmetallthiocyanaten
Zusammenfassung Es wurden 4,4-Dipyridylkomplexe des TypesLn(4-dipy)2(NCS)3·5H2O mitLn = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu und Y dargestellt. Die IR-Spektren und andere physikalische Eigenschaften werden diskutiert und die thermische Zersetzung von einigen Verbindungen (in der Reihe Gd ÷ Lu) untersucht.
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