Structural and thermal properties of rare earth complexes with 2,2′-biphenyldicarboxylic acid

Rare earth complexes with 2,2′-biphenyldicarboxylic acid (diphenic acid = H₂dpa) were obtained as hydrated precipitates of the general formula Ln₂(C₁₄H₈O₄)₃∙nH₂O, where n = 3 for the of Y(III) and Ce(III)–Er(III) and n = 6 for La(III), Tm(III), Yb(III) and Lu(III) complexes. On heating in air atmosphere complexes lose all water molecules in the temperature range 30–210 °C in one step and form anhydrous compounds, which are stable up to 315–370 °C. During further heating they decompose to oxides. The trihydrated compounds are crystalline powders whereas the hexahydrated are amorphous solids. The trihydrated complexes crystallize in the monoclinic (Pr(III) and Ce(III) complexes) and triclinic (Y(III) and Nd(III)–Er(III) complexes) crystal systems.     

Thermal and Spectral Features of Yttrium and Heavy Lanthanide Complexes with 2,4-dimethoxybenzoic Acid

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.     

Reactions and phases within the TeO2-rich part of the Bi2O3-TeO2 system

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.     

Preparation, Spectral and Thermal Studies of Y(III) and Lanthanide(III) 1-Hydroxy-2-Naphthoates

Complexes of lanthanide(III) (La–Lu) and Y(III) with 1-hydroxy-2-naphthoic acid were obtained as crystalline compounds with a general formula Ln[C₁₀H₆(OH)COO]₃⋅nH₂O:n=6 for La–Tm and Y, n=2 for Yb and n=0 for Lu. IR spectra of the prepared complexes were recorded, and their thermal decomposition in air were investigated. Spectroscopic data suggest that in the coordination of metal-organic ligand only oxygen atoms from the carboxylate group take part. When heated, the complexes decompose to the oxides Ln₂O₃, CeO₂, Pr₆O₁₁ and Tb₄O₇ with intermediate formation of Ln(C₁₁H₇O₃)(C₁₁H₆O₃). This revised version was published online in August 2006 with corrections to the Cover Date.     

Spectral and Thermal Studies of Rare Earth Complexes With 2,4,6-trimethylbenzoic Acid

The rare earth element 2,4,6-trimethylbenzoates were prepared as solids with the general formula Ln(C₁₀ H₁₁ O₂ )₃ ×n H₂ O, where n =2 for Ln =Y, La–Nd, and n =1 for Ln =Sm–Lu. The IR spectra of the complexes prepared were recorded and their solubilities in water and thermal decomposition in the air were investigated. During heating the hydrated complexes lose all the crystallization water molecules in one (Y, Ce–Lu) or two steps (La) and then the anhydrous complexes decompose either directly to oxides (Y, Ce, Pr, Sm–Lu) or with intermediate formation oxocarbonates Ln₂ O₂ CO₃ (La, Nd). The carboxylate groups in the complexes prepared act probably as mono- and bidentate. This revised version was published online in July 2006 with corrections to the Cover Date.     

New Complexes of Rare Earth Elements with 3-Methyladipic Acid

Rare earth element 3-methyladipates were prepared as crystalline solids with general formula Ln₂(C₇H₁₀O₄)₃⋅nH₂O, where n=6 for La, n=4 for Ce,Sm–Lu, n=5 for Pr, Nd and n=5.5 for Y. Their solubilities in water at 293 K were determined (2⋅10^–3–1.5⋅10^–4 mol dm^–3). The IR spectra of the prepared complexes suggest that the carboxylate groups are bidentate chelating. During heating the hydrated 3-methyladipates lose all crystallization water molecules in one (Ce–Lu) or two steps (Y) (except of La(III) complex which undergoes tomonohydrate) and then decompose directly to oxides (Y, Ce) or with intermediate formation of oxocarbonates Ln₂O₂CO₃ (Pr–Tb) or Ln₂O(CO₃)₂ (Gd–Lu). Only La(III) complex decomposes in four steps forming additionally unstable La₂(C₇H₁₀O₄)(CO₃)₂. This revised version was published online in August 2006 with corrections to the Cover Date.     

Complexes of Heavy Lanthanides and Yttrium with 3,4-dimethoxybenzoic Acid

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 μ_eff 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.     

Thermal and Spectral Studies of Y(III) and Lanthanide(III) Complexes with Mesaconic Acid

Y(III) and lanthanide(III) mesaconates were prepared as crystalline solids with general formula Ln₂(C₅H₄O₄)₃⋅nH₂O, where n=7 for La−Pr, n=4 for Y,Nd−Ho, n=8 for Er−Lu. IR spectra of the prepared mesaconates suggest that carboxylate groups are bidentate bridging anf chelating. During heating the hydrated complexes are dehydrated in one (Y, Nd−Lu) or two steps (La−Pr) and then decompose directly to oxides (Y, Ce, Pr, Sm, Gd−Lu) or with intermediate formation Ln₂O₂CO₃ (La, Nd, Eu). This revised version was published online in August 2006 with corrections to the Cover Date.     

Spectral and Thermal Studies of Rare Earth Element 3-methylglutarates

Conditions for the formation of rare earth element (Y, La–Lu) 3-methylglutarates were studied and their quantitative composition and solubilities in water at 293 K were determined (10^–2 mol dm^–3). The IR spectra of the prepared complexes with general formula Ln₂(C₆H₈O₄)₃ nH₂O (n=3–8) were recorded and their thermal decomposition in the air were investigated. During heating the hydrated 3-methylglutarates are dehydrated in one step and next anhydrous complexes decompose to oxides Ln₂O₃ with intermediate formation Ln₂O₂CO₃ (Y, La, Nd–Gd) or directly to the oxides, Ln₂O₃, CeO₂, Pr₆O₁₁ and Tb₄O₇ (Ce, Pr, Tb–Lu). This revised version was published online in August 2006 with corrections to the Cover Date.     

4-Chloro-2-methoxybenzoates of heavy lanthanides(III) and yttrium(III)

4-Chloro-2-methoxybenzoates of heavy lanthanides(III) and yttrium(III) were obtained as mono-, di-, tri-or tetrahydrates with metal to ligand ratio of 1:3 and general formula Ln(C₈H₆ClO₃)₃·nH₂O, where n=1 for Ln=Er, n=2 for Ln=Tb, Dy, Tm, Y, n=3 for Ln=Ho and n=4 for Yb and Lu. The complexes were characterized by elemental analysis, FTIR spectra, TG, DTA and DSC curves, X-ray diffraction and magnetic measurements. The carboxylate group appears to be a symmetrical bidentate chelating ligand. All complexes are polycrystalline compounds. The values of enthalpy, ΔH, of the dehydration process for analysed complexes were also determined. The solubilities of heavy lanthanide(III) 4-chloro-2-methoxybenzoates in water at 293 K are of the order of 10⁻⁴ mol dm⁻³. The magnetic moments were determined over the range of 76–303 K. The results indicate that there is no influence of the ligand field of 4f electrons on lanthanide ions and the metal ligand bonding is mainly electrostatic in nature.     

Thermal properties of lanthanide(III) complexes with 5-amino-1,3-benzenedicarboxylic acid

The complexes of yttrium(III) and lanthanides(III) with 5-amino-1,3-benzenedicarboxylic acid form two isostructural series of compounds and have the general formula Ln₂(C₈H₅O₄N)₃·nH₂O, where n = 13 for Y, La-Er and n=9 for Tm, Yb, Lu. They are insoluble in water and stable at room temperature. On heating in air or inert gas atmosphere they lose all water molecules in several steps. The anhydrous compounds are stable to about 400°C and next decompose to oxides.     

Thermal and spectroscopic investigations of new lanthanide complexes with 1,2,4-benzenetricarboxylic acid

The new 1,2,4-benzenetricarboxylates of lanthanide(III) of the formula Ln(btc)·nH₂O, where btc is 1,2,4-benzenetricarboxylate; Ln is La-Lu, and n=2 for Ce; n=3 for La, Yb, Lu; and n=4 for Pr-Tm were prepared and characterized by elemental analysis, infrared spectra and X-ray diffraction patterns. Polycrystalline complexes are isotructural in the two groups: La-Tm and Yb, Lu. IR spectra of the complexes show that all carboxylate groups from 1,2,4-benzentricarboxylate ligands are engaged in coordination of lanthanide atoms. The thermal analysis of the investigated complexes in air atmosphere was carried out by means of simultaneous TG-DTA technique. The complexes are stable up to about 30°C but further heating leads to stepwise dehydration. Next, anhydrous complexes decompose to corresponding oxides. The combined TG-FTIR technique was employed to study of decomposition pathway of the investigated complexes.     

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.

     

Synthesis,spectroscopic and thermal studies of 2,3-naphthalenedicarboxylates of rare earth elements

The complexes of rare earth elements with 2,3-naphthalenedicarboxylic acid of the formula: Ln₂(C₁₂H₆O₄)₃·nH₂O, where Ln = La(III)-Lu(III) and Y(III); n = 3 for La(III), Ce(III); n = 6 for Pr(III)-Yb(III) and Y(III) and n = 5 for Lu(III) have been synthesized and characterized by elemental analysis, IR spectroscopy, thermal analysis (TG, DTG, DTA and TG-FTIR) and X-ray analysis. They are sparingly soluble in water and stable at room temperature. During heating in air atmosphere, they lose all water molecules in several steps, generally in two or three steps, except for the La(III) and Ce(III) complexes which lose all water molecules in one step. The anhydrous compounds are stable up to about 773 K and then decompose to corresponding oxides. The thermal decomposition is connected with the release of water molecules (443 K), carbon dioxide (713 K) and hydrocarbons.     

Comparison of thermal properties of lanthanide trimellitates prepared by different methods

By diffusion in gel medium new complexes of formulae: Nd(btc)⋅6H₂O, Gd(btc)⋅4.5H₂O and Er(btc)·5H2O (where btc=(C₆H₃(COO)₃ ³⁻) were obtained. Isomorphous compounds were crystallized in the form of globules. During heating in air atmosphere they lose stepwise water molecules and then anhydrous complexes decompose to oxides. Hydrothermally synthesized polycrystalline lanthanide trimellitates form two groups of isomorphous compounds. The light lanthanides form very stable compounds of the formula Ln(btc)⋅nH₂O (where Ln=Ce−Gd and n=0 for Ce; n=1 for Gd; n=1.5 for La, Pr, Nd; n=2 for Eu, Sm). They dehydrate above 250°C and then immediately decomposition process occurs. Heavy lanthanides form complexes of formula Ln(btc)⋅nH₂O (_Ln=Dy−Lu). For mostly complexes, dehydration occurs in one step forming stable in wide range temperature compounds. As the final products of thermal decomposition lanthanide oxides are formed.     

Thermal decompositions of heavy lanthanide aconitates

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.     

Thermal properties of rare earth elements complexes with 1,3,5-benzenetricarboxylic acid

Summary Rare earth elements 1,3,5-benzenetricarboxylates were prepared as solids of the general formula Ln(C₉H₃O₆)·nH₂O, where n=6 for La-Dy and n=4 for Ho-Lu,Y. Their solubilities in water at 293 K are of the order 10^-4-10^-6 mol dm^-3. The IR spectra of the complexes indicate that the carboxylate groups are bridging and bidentate chelates. Hydrated 1,3,5-benzenetricarboxylates lose water molecules during heating in one step (La-Tb), two steps (Y, Ho-Tm) or three steps (Dy, Yb, Lu). The anhydrous complexes are stable up to 573-742 K and decompose to oxides (Ce-Lu) at higher temperatures.     

Studies on the Thermal Decomposition of Rare Earth Caproates

The thermal decomposition of rare earth caproates with general formula Ln(C₅H₁₁COO)₃ nH₂O, (where Ln=Y, La-Pr, n=l; Ln=Nd-Er, n=2; Ln=Tm-Lu, n=3) were studied in an air atmosphere. On heating, the hydrated caproates are dehydrated in one step and then the anhydrous complexes decompose to the oxides (Ln₂O₃, Pr₆O₁₁) with formation of the intermediate Ln₂O₂CO₃ (La, Pr-Gd) or directly to the oxides Ln₂O₃, CeO₂, Tb₄O₇(Y, Ce, Tb-Lu). Caproates of rare earth elements are liquefied during dehydration.     

Complexes of Y,La, and lanthanides withm-aminobenzoic acid

Summary m-Aminobenzoates of Y, La and lanthanides prepared in the reaction of the hydroxides of metal withm-aminobenzoic acid in solution have the general formulaLn(m-C₆H₄NH₂COO)₃·nH₂O wheren=4 for Ho, Tm,n=5 for Y, Sm, Dy, Er, Lu, andn=6 for La-Nd, Eu, Gd, Tb, Yb. The water molecules in the hydrated compounds are in the outer coordination sphere. On heating in air at 350–410 K dehydration occurs and anhydrousm-aminobenzoatesLn(m-C₆H₄NH₂COO)₃ are formed. On the basis of the IR spectra it was found that the metal in hydratedm-aminobenzoate of lanthanides is simultaneously coordinated through amino- and carboxyl groups whereas in anhydrousm-aminobenzoates of lanthanides only trough the bidentate carboxyl group. From X-ray analysis it was stated that the hydratedm-aminobenzoates of lanthanides are isostructural in the whole range Y, La-Lu.

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Komplexe von Y, La und Lanthaniden mitm-Aminobenzoesäure

Zusammenfassung Zur Darstellung der Verbindungen des TypsLn(m-C₆H₄NH₂COO)₃·nH₂O (mitn=4 fürLn=Ho, Tm,n=5 fürLn=Y, Sm, Dy, Er, Lu undn=6 fürLn=La-Nd, Eu, Gd, Tb, Yb) wurde die berechnete Menge vonLn(OH)₃ undm-C₆H₄NH₂COOH-Lösung bei 363 K gemischt und zur Kristallisation gebracht. Die Produkte wurden abfiltriert, mit Alkohol gewaschen und bis zur Gewichtskonstanz getrocknet. Die VerbindungenLn(m-C₆H₄NH₂COO)₃·nH₂O sind isostrukturell, mit geringer Löslichkeit in Wasser bei Raumtemperatur. Beim Erhitzen erfolgt zunächst Entwässerung bei 350–410 K, später bei 600–1 050 K unter Zersetzung zu CeO₂, Pr₆O₁₁, Tb₄O₇ undLn ₂O₃. Die Infrarotspektren der Verbindungen wurden registriert. Es wurde festgestellt, daß die Koordination der Seltenerdmetalle mit den Liganden sowohl durch Amino- als auch mit Carboxylgruppen erfolgt.

     

Spectroscopic and Thermal Studies of Rare Earth Element 4-Methylphthalates

Complexes of lanthanide(III) (La-Lu) and Y(III) with 4-methylphthalic acid were prepared and their IR spectra, solubility in water at 295 K and thermal decomposition were investigated. Rare earth complexes were obtained as solids with a 2:3 ratio of metal to organic ligand. COO^– groups in the prepared complexes act as bidentate chelating and bidentate bridging. During heating they are dehydrated in one (La-Tm) or twosteps (Yb, Lu and Y) and then decompose to the oxides Ln₂O₃, CeO₂, Pr₆O₁₁ and Tb₄O₇. This revised version was published online in July 2006 with corrections to the Cover Date.