Subject Index to Volume 21

Abstract

Time‐resolved laser‐induced fluorescence spectroscopy (TRLFS) was employed to determine the inner‐sphere (i.e., first coordination sphere) hydration number (N _H2O) of lanthanide(III) ions (Ln = Sm, Eu, Tb, and Dy) in the TRPO‐dodecane/HNO₃ (or HNO₃–NaNO₃) system under various conditions. In addition, the N _H2O of Ln(III) in extracted complexes with octyl(phenyl)‐N,N‐diisobutylcarbamoylmethyl phosphine oxide (CMPO), dihexyl‐N,N‐diethylcarbamoylmethyl phosphonate (CMP), trioctyl phosphine oxide (TOPO), and tributyl phosphate (TBP) were also determined. The results show that there is no water molecule in the first coordination sphere of Ln(III) complexes, except for Sm(III) and Dy(III) in CMP complexes.     

Synergistic Solvent Extraction of Lanthanides(III) with Mixtures of 4-benzoyl-3-methyl-1-phenylpyrazol-5-one and Some Novel Carbamoyl- and Phosphorylmethoxymethylphosphine Oxides

The solvent extraction of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y from weak acidic hydrochloric acid solutions into an organic phase containing 4-benzoyl-3-methyl-1-phenylpyrazol-5-one (HP) and neutral tridentate organophosphorus ligands R₂P(O)CH₂OCH₂C(O)NBu₂ R = Bu (I), R = Ph (II) and R₂P(O)CH₂OCH₂P(O)R¹₂ R = R¹ = Bu (III); R = Bu, R¹ = Ph (IV); R = R¹ = Ph(V) has been studied. A considerable synergistic effect was observed in the presence of HP in the organic phase containing tetraoctyldiglycolamide (TODGA) and neutral organophosphorus ligands I - V. A successive replacement of C(O)NAlk₂ groups in the diglycolamide extractant molecule by P(O)Ph₂ groups leads to an increase in the extraction efficiency of Ln(III) ions when toluene was used as diluent. Phosphoryl-containing podand I possess a higher extraction efficiency towards Ln(III) ions than TODGA. The extraction equilibrium was investigated and the equilibrium constants were calculated. It was found that the lanthanide(III) ions are extracted as LnLP₃ and LnL₂P₃ complexes with mixtures of HP and I in toluene from weak acidic solutions.     

Synergistic Extraction of Lanthanides(III) by Mixtures of N‐p‐Methoxybenzoyl‐N‐phenylhydroxylamine and 1,10‐Phenanthroline

Abstract

We conducted a study on the equilibrium extraction behavior of the trivalent lanthanide ions (M³⁺), La, Pr, Eu, Ho, and Yb, from tartrate aqueous solutions into chloroform solutions containing N‐p‐methoxybenzoyl‐N‐phenylhydroxylamine (Methoxy‐BPHA, HL) and 1,10‐phenanthroline (phen). The synergistic species extracted was found to be {ML₂(phen) (HL)}⁺(1/2)Tar^2?, where Tar^2? is tartrate ion. The extraction constants were calculated. The extraction separation behavior and extractability of lanthanides are discussed in comparison with the self‐adducted chelate, ML₃(HL)₂, which was extracted in the absence of phen, and synergistic extraction by mixtures of other extractants such as 2‐thenoyltrifluoroacetone, and neutral donors.     

Monometallic and bimetallic europium(III) and terbium(III) complexes: Synthesis and luminescent properties

Eight new lanthanide complexes of the form Ln(L)₃bipy and [Ln(L)₃]₂bpm were synthesized (where L = 2,2,6,6-tetramethyl-3,5-heptanedione (tmh) and 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione (tdh), bipy = 2,2′-bipyridine, bpm = 2,2′-bipyrimidine and Ln = Tb(III) or Eu(III)). The luminescent spectra are typical of Tb(III) and Eu(III) complexes with intense transitions at 545 nm for Tb(III) and 612 nm for the Eu(III) complexes. Energy gaps between the tmh 1 orbitals and the ⁰D_J manifold of Eu(III) are too large to give efficient energy transfer therefore emission spectra for Eu(tmh)₃bipy and [Eu(tmh)₃]₂bpm were not detected. Lifetimes are greatest for the Tb(III) complexes containing tmh terminal ligands while the longest lifetimes for the Eu(III) complexes occur with the tdh terminal ligands.     

Synergistic Solvent Extraction and Separation of Lanthanide(III) Ions with 4‐Benzoyl‐3‐Phenyl‐5‐Isoxazolone and the Quaternary Ammonium Salt

The solvent extraction of the lanthanide(III) ions (without Pm) with a 4‐benzoyl‐3‐phenyl‐5‐isoxazolone(HPBI) alone and in the presence of the quaternary ammonium salt Aliquat 336 in perchlorate form (QClO₄) in C₆H₆ was investigated by the slope analysis method. The composition of the extracted species was determined as Ln(PBI)₃ and Q[Ln(PBI)₄] (Q⁺ is the quaternary ammonium salt cation). The values of the equilibrium constant were calculated. Synergistic effects were found for all lanthanide metals when they were extracted with a binary mixture of HPBI and QClO₄. The influence of the synergistic agent on the extraction process has been discussed. The parameters of the extraction process were determined. The separation factors between adjacent metals were evaluated.     

Synergistic Extraction of U(VI), Th(IV), and Lanthanides(III) from Nitric Acid Solutions Using Mixtures of TODGA and Dinonylnaphthalene Sulfonic Acid

The extraction of U(VI), Th(IV), and lanthanides(III) from aqueous nitric acid solutions with mixtures of N,N,N′,N′-tetra(n-octyl)diglycolamide (TODGA) and dinonylnaphtalene sulfonic acid (HDNNS) in n-decane has been investigated. The extraction efficiency of U(VI), Th(IV), and Ln(III) ions is greatly enhanced by addition of HDNNS to an organic phase containing TODGA. The synergistic effect arises from the higher hydrophobicity of U(VI), Th(IV), and Ln(III) extracted species formed by TODGA and DNNS^? anions as compared to those formed by TODGA and NO₃^? ions as counter anions. The synergistic effect for U(VI), Th(IV), and Ln(III) extraction from aqueous nitric acid solutions with mixtures of TODGA and HDNNS becomes weaker when the acidity of the aqueous phase increases. A high synergistic enhancement is accompanied with a high selectivity of Ln(III) extraction from nitric acid solutions.     

Synthesis,Characterization and Fluorescence Properties of Poly(styrene-co-n-caprylamide maleic acid) and Its Europium(III) and Terbium(III) Complexes

Copolymer of poly(styrene-co-n-caprylamide maleic acid) (PSCMA, defined as HL) and its lanthanide complexes Ln(L)₃·6H₂O (Ln = Eu and Tb) had been synthesized and characterized by elemental analysis, X-ray diffraction, Fourier transform infrared spectra, UV-spectrophotometer and thermal analysis (TG–DTA). The fluorescence properties of the HL ligand and the Ln(L)₃·6H₂O complexes in the solid state were investigated. At room temperature, the HL ligand had a strong broad emission band at 410–575 nm (λmax = 458 nm) under excitation at 380 nm, while the respective characteristic emission of Eu(III) and Tb(III) ions was observed in Ln(L)₃·6H₂O complexes. This demonstrated that the HL ligand in the extra-framework channels succeeded in sensitizing Eu(III) and Tb(III) ions emission. Compared with the Eu(L)₃·6H₂O complex, the fluorescence intensity of the Tb(L)₃·6H₂O complex was much stronger. This indicated that the lowest excited triplet state energy level of HL matched well with the excited state energy level of Tb(III). With the increase of the Ln(III) ions content below 15 wt%, the fluorescence intensity increased monotonically. All the Ln(L)₃·6H₂O complexes exhibited high quantum yield, long fluorescence lifetime and good thermal stability.     

Investigation into Coordination States of Diglycolamide and Dioxaoctanediamide Complexes with Lanthanide Elements Using Spectroscopic Methods

The extraction behavior and complexation state of diglycolamide (DGA) and dioxaoctanediamide (DOODA) ligands were investigated for several trivalent lanthanide ions (Ln(III)). The stoichiometry of the extraction of La(III), Nd(III), and Ho(III) with the hydrophobic ligands, N,N,N’,N’-tetraoctyl diglycolamide (TODGA) and N,N,N’,N’-tetraoctyl dioxaoctanediamide (DOODA(C8)), was determined by slope analyses in CHCl₃ and CCl₄ system. Ultraviolet-visible (UV-Vis) spectroscopy was employed for determination of the stability constants (β) of trivalent lanthanide ion (Ln³⁺) with the hydrophilic ligands, N,N,N’,N’-tetraethyl diglycolamide (TEDGA) and N,N,N’,N’-tetraethyl dioxaoctanediamide (DOODA(C2)). DGA ligands are found to have an affinity of heavier Ln(III), while DOODA ligands prefer to coordinate with lighter Ln(III). Infrared (IR) and nuclear magnetic resonance (NMR) spectroscopic measurements reveal that the carbonyl oxygen atoms of TODGA and DOODA(C8) worked as dominant donors in complexation with La(III). In contrast, the ether oxygen of the hydrophilic ligands makes major contribution to formation of La(III) complex.     

Interactions of trivalent lanthanide cations with tetradentate Schiff bases. Synthesis and characterization of lanthanide(III) complexes with N,N′-bis(pyridin-2-ylmethylene)benzene-1,2-diamine

The novel lanthanide(III) complexes [La(NO₃)₃(H₂O)L] 1, and [Ln(NO₃)₃L] (Ln=Pr 2, Sm 3, Gd 4) where L=N,N^′-bis(pyridin-2-ylmethylene)benzene-1,2-diamine, have been obtained by direct reaction of the Schiff base ligand and the corresponding hydrated lanthanide(III) nitrates in methanol. All complexes were characterized spectroscopically and thermogravimetrically. Complex 3 was also characterized with crystallographic studies. In the molecular structure of 3, Sm(III) is surrounded by all four nitrogen atoms of the Schiff base and six oxygen atoms belonging to three bidentate chelating nitrato ligands.     

Extraction of Lanthanides(III) with N,N′-Bis(Diphenylphosphinyl-Methylcarbonyl)Diaza-18-Crown-6 in the Presence of Ionic Liquids

The extraction of microquantities of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y from nitric acid solutions into an organic phase containing N,N′-bis(diphenylphosphinyl-methylcarbonyl)diaza-18-crown-6 and ionic liquid (IL) 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide (BMImTf₂N) has been studied. The effect of HNO₃ concentration in the aqueous phase and that of the extractant and IL concentration in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes has been determined. A considerable synergistic effect was observed in the presence of IL in the organic phase containing a neutral organophosphorus ligand. This effect is connected with the hydrophobic nature of the IL anion. The partition of IL between the equilibrium organic and aqueous phases is the dominant factor governing the extractability of lanthanide (III) ions in the extraction system. The potentialities of polymeric resin impregnated with compound I and BMImTf₂N for the preconcentration of lanthanides(III) from nitric acid solutions are demonstrated.     

Complexation of Eu(III) with Dibutyl Phosphate and Tributyl Phosphate

Abstract

The complexation of Ln(III) with tributyl phosphate (TBP) in the presence of dibutyl phosphate (HDBP) is of importance for the smooth operation of the plutonium uranium refining extraction (PUREX) process. The time resolved laser‐induced fluorescence spectroscopy (TRLFS) and extraction experiments were employed to study the complexation of Eu(III) with TBP or HDBP and their mixture. The emphasis was on the inner‐sphere hydration numbers and emission spectra of the Eu(III) extracted complexes. The results show that the HNO₃ loading in the organic phase influences not only the distribution ratio but also the emission spectra, as well as the hydration numbers of the complexes. For the Eu‐TBP complexes, one water molecule remained at low HNO₃ loading in the organic phase, and it would be removed at enhanced HNO₃ loading. For the Eu‐HDBP complexes, one water molecule remained at low or high HNO₃ loading. For the Eu‐HDBP/TBP or Eu‐HDBP/30%TBP, more than one species formed and third phase with different chemical form appeared at low HNO₃ loading. The possible species of Eu(III) complexes formed under various conditions were proposed and discussed.     

Synergistic Extraction of Lanthanides(III) with N‐p‐Methoxybenzoyl‐N‐Phenylhydroxylamine and Neutral Nitrogen Donors

Abstract

We investigated the extraction equilibrium behavior of a series of trivalent lanthanide ions, (M³⁺), La, Pr, Eu, Ho, and Yb, from tartrate aqueous solutions using a chloroform solution containing N‐p‐methoxybenzoyl‐N‐phenylhydroxylamine (Methoxy‐BPHA or HL) combined with an adductant, 1,10‐phenanthroline (phen) or 2,2′‐bipyridyl (bipy). The synergistic species extracted were found to be {ML₂(phen)(HL)}⁺(1/2)Tar^2? and {ML₂(bipy)(HL)₂}⁺(1/2)Tar^2?, where Tar^2? is the tartrate ion. The stoichiometry, the extraction constants, and the separation factors of these systems were determined. We discuss the extractability and the separation factors in comparison with self‐adduct chelates, ML₃(HL)_2,(o), which were formed in the absence of phen or bipy.     

SYNERGISTIC SOLVENT EXTRACTION OF LANTHANIDES WITH MIXTURES OF 1-PHENYL-3-METHYL-4-BENZOYL-PYRAZOL-5-ONE AND ALIQUAT 336

The solvent extraction of Pr(III),Gd(III) and Yb(III) With 1-phenyl-3-methyl-4-benzoyl-pyrazol-5-one (HP) and Aliquat 336(QCl) in CCl₄.C₆H₆ and CHCl₃, has been studied.The composition of the extracted species has been determined as LnP₄ ^?.Q⁺ (Ln=Pr,Gd and Yb).The values of the equilibrium constants have been calculated. The extraction mechanism has been discussed.     

Extraction of U(VI), Th(IV), and Lanthanides(III) from Nitric Acid Solutions with CMPO-Functionalized Ionic Liquid in Molecular Diluents

The extraction of microquantities of U(VI), Th(IV), and lanthanides(III) from nitric acid solutions with CMPO-functionalized ionic liquid 1-[3[[(diphenylphosphinyl)acetyl]amino]propyl]-3-tetradecyl-1H-imidazol-3-ium hexafluorophosphate, CMPO-FIL(I) in molecular organic diluents has been studied. The effect of HNO₃ concentration in the aqueous phase and that of extractant concentration in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes was determined. CMPO-FIL(I) demonstrates greater extraction ability towards Ln(III) than its neutral CMPO analog, diphenylphosphorylacetic acid N-nonylamide. This inner synergistic effect increases with a decreasing organic diluent polarity. The partition of CMPO-FIL(I) between the equilibrium organic and aqueous phases is the dominant factor governing the extractability of Ln(III) ions in the extraction system.     

DISTRIBUTION EQUILIBRIUM OF LANTHANIDE(III) COMPLEXES WITH N-BENZOYL-N-PHENYLHYDROXYLAMINE IN SEVERAL INERT SOLVENT SYSTEMS

ABSTRACT

The distribution equilibrium of lanthanides(III) (Ln) with N-benzoyl-N-phenylhydroxylamine (BPHA, HL) in several inert solvent systems was studied. The representative lanthanides(III) (Yb, Eu and Pr) were all found to extract as self-adduct chelates of the form, LnL3(HL)m, (m = 1–3), containing a different number of neutral adduct molecules in extracted species. The differences in the number of neutral adduct molecules in extracted species with each solvents are attributed to the difference in the solvation trend for BPHA. The extraction constant and separation factor were determined in several inert solvent systems. It was found that the distribution ratio of lanthanide(III) tends to decrease with increases in the distribution constant of BPHA. Relationship between the polarity of the solvent and the extractability are also discussed.     

Formation of W/O Microemulsions in the Extraction of the Lanthanide Series by Purified Cyanex 301

The formation of water-in-oil (W/O) microemulsions during the extraction of the series of trivalent lanthanides Ln(III) by bis(2,4,4-trimethylpentyl)dithiophosphinic acid (HC301, also known as purified Cyanex 301) was studied. The phenomena in the formation of W/O microemulsions were similar in the extraction of all Ln(III) by HC301 at a high neutralization degree (50%), according to the measurement of the distribution ratios of Ln(III) and the concentrations of Na⁺ and NO₃^- in the organic phase, IR spectroscopy, and dynamic light scattering (DLS). W/O microemulsions also formed at a low neutralization degree (15%) for the extraction of heavy Ln(III). The coordination environment of the representative heavy lanthanide Ho(III) in the extracted complexes was monitored by absorption spectroscopy and extended X-ray absorption fine structure (EXAFS). Unlike the light lanthanide, Nd(III) and Ho(III) in the organic phase did not directly coordinate with the HC301 anions regardless of whether W/O microemulsions formed, which further demonstrated the different extraction behavior of HC301 toward the light lanthanides and the heavy lanthanides.     

Equilibrium and spectroscopic studies on the complexation of tris(1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedionato)lanthanoids(III) with tris(2,4-pentanedionato)cobalt(III) as complex ligand

Complexation equilibrium between tris(1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedionato)lanthanoids(III) (Ln(tta)₃, Ln=La, Eu, and Lu) and tris(2,4-pentanedionato)cobalt(III) (Co(acac)₃) has been studied by the liquid–liquid distribution technique. A 1:1 adduct of [Ln(tta)₃Co(acac)₃], i.e., a binuclear complex, was formed in benzene, and the stability constants were determined to be 10^4.64, 10^2.95, and 10^2.07 for La, Eu, and Lu respectively. The molar absorptivity of Co(acac)₃ for the ¹T_1g←¹A_1g transition increased with the adduct formation with Ln(tta)₃ in the order of Lu≪Eu<La. A ⁵⁹Co NMR study showed that a resonance of Co(acac)₃ shifted to the higher field with the adduct formation. The chemical exchange between free and complexed Co(acac)₃ was very slow in La but fast in Lu, while both the slow- and fast-exchange species existed in Eu.     

Synthesis and electrochemistry of acetylacetonatolanthanide(III)- phthalocyaninates

The synthesis and electrochemistry of acetylacetonatolanthanide(III)phthalocyaninates are reported. Two new kinds of lanthanide complexes Li[Pc]Ln(acac)₂] and (Pc)Ln(acac) were obtained where Ln is the trivalent ions of Eu, Gd, Dy, Tb, Ho, Er, Tm, Lu, and Pc is the dianion of phthalocyanine and acac is the acetylacetonate anion. These complexes were characterized by infrared and electronic absorption spectroscopy. An overall oxidation reduction mechanism at a platinum electrode in dimethyl sulfoxide is presented.     

Synthesis, structures, and photoluminescent properties of 3D lanthanide coordination polymers with rare (4,5)-connected topology

Three lanthanide coordination polymers, [Ln(Hpdc)(ox)_0.5(H₂O)₂]·H₂O (Ln = Nd(1), Eu(2), Er(3)) (H₃pdc = 3,5-pyrazoledicarboxylic acid, ox = oxalate), have been synthesized by the hydrothermal reaction of lanthanide nitrates, 3,5-pyrazoledicarboxylic acid, and oxalic acid (H₂ox) and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction studies indicate that complexes 1–3 are isomorphous and exhibit three-dimensional metal–organic frameworks with uncommon (4,5)-connected topology, which contain open channels occupied by the lattice water molecules. The photoluminescent properties of complex 2 were also studied.