Understanding the Complexation of Alkyl-Substituted Nitrilotriacetamides with Uranium: A Study by Absorption Spectroscopy and Microcalorimetry.

Complexation thermodynamics of UO22+ ions with a series of alkyl-substituted nitrilotriacetamides (NTA) was investigated by absorption spectroscopy and microcalorimetry. The hexamethyl derivative of NTA (HMNTA) forms the weakest two successive complexes with UO22+ ions with stability constants of log ß11 = 3.5 ± 0.1 and log ß12 = 6.1 ± 0.1. The formation constant values increased linearly with increasing alkyl chain length of the substituents from hexamethyl NTA to hexabutyl NTA (HBNTA) and to hexahexyl NTA (HHNTA). The complexation with each ligand was both enthalpy and entropy driven with exothermic enthalpy changes of ΔH11 = -14.7 ± 1.0 kJ/mol, ΔH12 = -10.2 ± 0.8 kJ/mol for HMNTA, ΔH11 = -19.2 ± 1.2 kJ/mol, ΔH12 = -16.4 ± 1.1 kJ/mol for HBNTA, and ΔH11 = -21.3 ± 1.4 kJ/mol, ΔH12 = -19.4 ± 2.3 kJ/mol for HHNTA. Similarly, the positive entropy changes with each ligand were ΔS11 = 18.1 ± 2.7 J/mol/K, ΔS12 = 82.9 ± 3.8 J/mol/K for HMNTA, ΔS11 = 14.4 ± 1.2 J/mol/K, ΔS12 = 87.2 ± 4.2 J/mol/K for HBNTA, and ΔS11 = 16.1 ± 2.4 J/mol/K, ΔS12 = 92.6 ± 3.1 J/mol/K for HHNTA. Structural features of the complex suggest the participation of two ligands coordinating in a bidentate mode via the carbonyl oxygens. The [UO2L2]2+ complexes appear to be noncentrosymmetric with two ligands and one water molecule occupying the equatorial plane of the dioxo uranyl cation. The structure of the complex was confirmed by 1H NMR titration, EXAFS measurements, and DFT calculations.

Understanding the Interaction of Uranyl Cation with Two C-Pivot Tripodal Amides: Synthesis, Complexation, Microcalorimetry, and DFT Studies.

Complexation of uranyl ions with two structurally related C-pivotal tripodal amides with varying spacer lengths, synthesized for the first time, was studied by optical spectroscopy. In the tripodal amides, the coordination was through the carbonyl O atoms where the carbonyl groups were away from the central C-atom by three spacer atoms (LI) and four spacer atoms (LII), respectively. Increasing the spacer atoms going from LI to LII favors the complexation with the linear uranyl cations and results in stronger complex formation. The complexation heat between the uranyl cations and the two amide ligands was directly measured by microcalorimetric titrations. The complexation with both the ligands was driven by exothermic enthalpy and positive entropy changes. Formation of the complex proceeded by the replacement of water molecules from the primary coordination sphere of the uranyl cation. Both ligands formed bisolvated (ML2-type) complexes in which one unit of the ligand binds in a monodentate manner and the other in a bidentate mode. Density functional theory calculations further supported our experimental observations.

Efficient actinide sequestration with ionic liquid-based extraction chromatography resins containing Aza-crown ether functionalized diglycolamides.

Two new extraction chromatographic resins (ECRs) were prepared by impregnating two exotic diglycolamide (DGA) ligands (having three or four DGA moieties tethered to aza-crown ether scaffolds) dissolved in an ionic liquid onto an inert solid support. A room temperature ionic liquid (RTIL) was used for enhancing the performance of the ECRs. The ECR containing triaza-9-crown-3 functionalized with three DGA moieties (TAM-3-DGA), and tetraaza-12-crown-4 tethered with four DGA arms (TAM-4-DGA) were evaluated for the separation of Am3+ and Pu4+from nitric acid solutions. The resin capacity for Eu3+ was 9.52 mg/g and 7.24 mg/g for TAM-3-DGA and TAM-4-DGA resins, respectively. Similarly, the resin capacity for Pu4+was 7.44 mg/g and 5.72 mg/g for TAM-3-DGA and TAM-4-DGA resins, respectively. These maximum loading values corresponded to the formation of a 1:1 metal/ligand complex for the Eu3+ ion and a 1:2 metal/ligand complex for the Pu4+ ion. The sorption of Eu3+and Pu4+on the resins followed a chemisorption phenomenon on both resins. The sorbed Eu3+and Pu4+ions from the resin phase could be efficiently desorbed with complexing ligands such as guanidine carbonate/HEDTA and oxalic acid, respectively.

Stability of composite polymeric beads containing a calix[4]arene-mono-crown-6 ligand for radio-cesium separation.

Bis-octyloxy-calix[4]arene-mono-crown-6 (BOCMC) is a selective ligand for Cs(I) cation, and has been used in solvent extraction method for its separation from acidic feed. Looking at the various advantages and ease of extraction chromatography separation method, an attempt was made to prepare stable composite beads containing BOCMC entrapped in a suitable polymeric matrix. Therefore, an attempt was made to prepare a series of composite polymeric beads containing BOCMC in polysulfone (PS), polyether sulfone (PES) and sodium alginate polymeric matrix. Preparations of the beads were attempted by dissolving the solid BOCMC in the polymer solution, and also by using the ligand solution in isodecanol/dodecane and ionic liquids and then mixing in the polymeric solution. Every attempt failed to get the desired quality of beads in PES and sodium alginate matrix. However, very good quality and stable beads were obtained when 25 mM ligand solution dissolved in C8mim.Tf2N ionic liquid was used in PS matrix. Detail study for the extraction chromatography separation of Cs(I) was studied with BOCMC/C8mim.Tf2N/PS composite beads. Detail investigations on the preparation, characterization, reusability and radiation stability of these beads have been studied and reported in details.

Metal-organic frameworks as superior porous adsorbents for radionuclide sequestration: Current status and perspectives.

Efficient separation of hazardous radionuclides from radioactive waste remains a challenge to the global acceptance of nuclear power due to complex nature of the waste, high radiotoxicities and presence of large number of interfering elements. Sorption of radioactive elements from liquid phase, gas phase or their solid particulates on various synthetic organic, inorganic or biological sorbents is looked as one of the options for their remediation. In this context, highly porous materials, termed as metal-organic frameworks (MOFs), have shown promise for efficient capturing of various types of radioactive elements. Major advantages that have been advocated for the application of MOFs in radionuclide sorption are their excellent chemical stability, and their large surface area due to abundant functional groups, and porosity. In this review, recent developments on the application of MOFs for radionuclide sequestration are briefly discussed. Focus has been devoted to address the separation of few crucial radioactive elements such as Th, U, Tc, Re, Se, Sr and Cs from aqueous solutions, which are important for liquid radioactive waste management. Apart from these radioactive metal ions, removal of radionuclide bearing gases such as I2, Xe, and Kr are also discussed. Aspects related to the interaction of MOFs with the radionuclides are also discussed. Finally, a perspective for comprehensive investigation of MOFs for their applications in radioactive waste management has been outlined.

Highly efficient plutonium scavenging by an extraction chromatography resin containing a tetraaza-12-crown-4 ligand tethered with four diglycolamide pendent arms.

An efficient extraction chromatography resin, containing tetraaza-12-crown-4 functionalized with four diglycolamide moieties, was evaluated for the separation of plutonium. This chromatography resin yielded very large distribution coefficients for Pu4+ (>105) in 0.5 - 6 M HNO3 feed solutions. Various physicochemical properties such as sorption kinetics, Pu4+ sorption mechanism, and its sorption capacity were investigated. The sorption kinetics, following a pseudo-second-order model, showed that about 10 minutes of equilibration was sufficient for >99.9% sorption of Pu4+. The sorption of Pu4+ on the resin followed the Langmuir monolayer model, which was confirmed by a theoretical calculation based on the kinetic model. The Pu4+ sorption on the resin was driven by a large exothermic enthalpy change (ΔH = -31.4±2.2 kJ/mol) and a positive entropy change (ΔS = 224±15 J/mol/L). The resin could sorb a maximum of 12.1±0.8 mg of Pu per gram of resin, which is equivalent to 1:2 metal/ligand complex on the resin. The Pu4+ from the resin phase was completely stripped with 0.5 M oxalic acid. A possible application of this resin for the separation / pre-concentration of Pu4+ was successfully demonstrated in the column mode.

Actinide ion uptake from acidic radioactive feeds using an extraction chromatographic resin containing a branched dialkyl amide.

A dialkyl amide with branched alkyl group, viz. N,N-di(2-ethylhexyl)-propionamide (D2EHPrA) was used as the organic extractant in an extraction chromatographic resin prepared for the first time and evaluated for the separation of uranium from acidic feeds. The distribution coefficient measurements, carried out at varying HNO3 concentrations, indicated an increase in the UO22+ ion sorption with increasing nitric acid concentration. The UO22+ ion sorption kinetics and sorption isotherms with this resin were investigated in details. The column studies indicated that 8.3 mg of uranium could be loaded on a 2.1 cm3 column bed volume containing 0.35 g resin. Batch distribution data for other actinides such as Np4+ and Pu4+ indicated that the resin can also be used for effective separation of these metal ions from acidic feeds. Though the resin showed effectiveness for Np and Pu, detailed investigations dealing with macro concentrations of metal ions (in gm quantities) were restricted to uranium only due to hazardous nature of plutonium and limited availability of neptunium. The encouraging results reported in this work is an indication of the possible application of this resin for the recovery or pre-concentration of UO22+, Np4+ and Pu4+ ions from large volumes of aqueous solutions of moderate acidity.

Highly efficient actinide(III)/lanthanide(III) separation by novel pillar[5]arene-based picolinamide ligands: A study on synthesis, solvent extraction and complexation.

Selective extraction of highly radiotoxic actinides(III) is an important and challenging task in nuclear wastewater treatment. Many proposed ligands containing S or P atoms have drawbacks including high reagent consumption and possible secondary pollution after incineration. The present work reports five novel pillar[5]arene-based extractants that are anchored with picolinamide substituents of different electronic nature by varying spacer. These ligands reveal highly efficient separation of actinides(III) over lanthanides(III). Specifically, almost all of these ligands could extract Am(III) over Eu(III) selectively at around pH 3.0 (SFAm/Eu>11) with fast extraction kinetics. Variation of the pyridine nitrogen basicity via changing para-substitution leads to an increase in the distribution ratios by a factor of over 300 times for Am(III) with an electron-withdrawing group compared to those with an electron donating group. Investigation of complexation mechanism by slope analysis, NMR, IR, EXAFS, and DFT techniques indicates that each ligand binds two metal ions by pyridine nitrogen and amide oxygen. Finally, these ligands do not show obvious decrease in both extraction and separation ability after being exposed to 250 kGy absorbed gamma radiation. These results demonstrate the potential application of pillar[5]arene-picolinamides for actinide(III) separation.

Unfolding the complexation and extraction of Am3+ and Eu3+ using N-heterocyclic aromatic diphosphonic acids: a combined experimental and DFT study.

Phosphonate based ligands are well known for the extraction of 'f' block elements. Three N,O-donor N-heterocyclic aromatic diphosphonate ligands were evaluated in the present work for the extraction/separation studies of Am3+ and Eu3+. Complexation studies in aqueous medium using luminescence titration indicated the formation of anionic complexes in the case of Eu3+. Two phase liquid-liquid extraction studies were, therefore, carried out by employing Aliquat-336 as the liquid anion exchanger. The results indicated the formation of a species with a metal-ligand stoichiometry of 1 : 3 in the case of pyridine-2,6-diphosphonic acid (PyPOH). In the case of 2,2'-bipyridine-6,6'-diphosphonic acid (BipyPOH), however, a 1 : 2 complex was extracted and 1,10-phenanthroline-2,9-diphosphonic acid (PhenPOH) extracts the Am3+ and Eu3+ ions by forming both 1 : 2 and 1 : 3 complexes. Formation of these kinds of anionic complexes was further confirmed using electrospray ionization mass spectrometry (ESI-MS). DFT calculations predicted the structure of the anionic complexes. The non-selectivity of these kinds of ligands between Am3+ and Eu3+ was attributed to the presence of unfavorable covalent interactions in the metal-ligand bonds.

Highly Efficient N-Pivot Tripodal Diglycolamide Ligands for Trivalent f-Cations: Synthesis, Extraction, Spectroscopy, and Density Functional Theory Studies.

A series of four N-pivot tripodal diglycolamide (DGA) ligands, where three DGA moieties are attached to the central N atom via spacers of different lengths and with varying alkyl substituents on the amidic nitrogen of DGA (LI-LIV), were studied for their extraction and complexation ability toward trivalent lanthanide/actinide ions, including solvent extraction, complexation using spectrophotometric titrations, and luminescence spectroscopic studies. Introduction of a methyl group on the amidic nitrogen atom gives rise to a 400 fold increase of the Eu distribution ( D) value [LIII (NMe) vs LII (NH)] at 1 M HNO3. Enlargement of the spacer length between the pivotal N atom and the DGA moieties with one carbon atom results in a 14 times higher DEu value [LI (C3) vs LII (C2)]. Slope analyses showed that Eu3+ was extracted as a bis-solvated species with all four ligands. The compositions of the Eu3+/L complexes were further confirmed by spectroscopic measurements, its formation constants following the order: LIII > LIV > LI > LII. Luminescence spectroscopy and electrospray ionization mass spectrometry revealed that all four ligands form [Eu(L)2(NO3)3] complexes. Density functional theory and thermodynamic parameters corroborated the existence of [Eu(L)2(NO3)3] complexes.

Evaluation of two aza-crown ether-based multiple diglycolamide-containing ligands for complexation with the tetravalent actinide ions Np4+ and Pu4+: extraction and DFT studies.

Two multiple diglycolamide (DGA)-containing extractants where the DGA arms are tethered to the nitrogen atoms of two aza-crown ether scaffolds, a 9-membered aza-crown ether containing three 'N' atoms (LI) and a 12-membered aza-crown ether containing four 'N' atoms (LII), were evaluated for the extraction of the tetravalent actinide ions Np4+ and Pu4+. The tripodal ligand with three DGA arms (LI) was relatively inferior in its metal ion extraction properties as compared to the tetrapodal ligand with four DGA arms (LII) and Pu4+ ion was better extracted than Np4+ ion with both the ligands. A solvation extraction mechanism, where species of the type ML(NO3)4 are extracted, was found to be operative for both the ligands involving both the tetravalent actinide ions. While the extraction of the metal ions increased with the feed nitric acid concentration up to 4 M, a sharp decline in the extraction was seen after that. Quantitative extraction (>99%) of the actinide ions was observed with LII from 4 M HNO3, suggesting the possible application of the ligands for actinide partitioning of high-level waste. The structure and the composition of the complexes were optimized by DFT computations.

Effect of an alkyl substituent and spacer length in benzene-centered tripodal diglycolamides on the sequestration of minor actinides.

Three benzene-centered tripodal diglycolamide (Bz-T-DGA) ligands, where diglycolamide (DGA) moieties are tethered to the central benzene ring through a methylene spacer and having either a hydrogen atom (LI) or an isopentyl group (LII) attached to the N-atom, and DGA moieties attached via an ethylene spacer and having an isopentyl group attached to the N-atom (LIII), were studied for their complexation and extraction abilities towards trivalent actinides and lanthanides. The distribution ratio of Am(iii) and Eu(iii) with 1 mmol L-1 ligand in 5% iso-decanol/n-dodecane followed the order: LII > LIII > LI. The substitution of the H atom with the isopentyl group on the N-atom of the DGA moieties resulted in two orders of magnitude enhancement in the extraction ability of the ligand. On the other hand, increase in the spacer length between the benzene ring and the DGA moieties resulted in several fold reduction in the extraction ability of the ligand. Spectroscopic studies with Eu3+ ions in acetonitrile also confirmed the metal/ligand complex formation constant in the order: LII > LIII > LI. Luminescence decay lifetimes of Eu3+/ligand complexes confirmed the absence of water molecules and that all the primary coordination sites of the metal ion are occupied by the ligands.

Liquid-liquid extraction and facilitated transport of f-elements using an N-pivot tripodal ligand.

Diglycolamide (DGA)-functionalized tripodal ligands offer the required nine-coordinated complex for effective binding to a trivalent lanthanide/actinide ion. A N-pivot tripodal ligand (TREN-DGA) containing three DGA pendant arms was evaluated for the extraction and supported liquid membrane transport studies using PTFE flat sheets. Solvent extraction studies indicated preferential extraction of 1:1 (M:L) species, while the metal ion extraction increased with increasing HNO3 concentration conforming to a solvated species extraction. Flat sheet-supported liquid membrane studies, carried out using 4.0 × 10-3 M TREN-DGA in 95% n-dodecane + 5% iso-decanol indicated faster mass transport for Eu3+ ion as compared to Am3+ ion. The determined transport parameters indicated slow diffusion of the M-TREN-DGA (M = Am or Eu) complex being the rate-determining step. The transport of lanthanides and actinides followed the trend: Eu3+ > Am3+∼ Pu4+ >> UO22+ and Am can be selectively separated from a mixture of U and Pu by oxidizing the latter to its +6 oxidation state. The liquid membrane stability was not encouraging and was deteriorating the transport efficiency with time, which was attributed to carrier loss into the aqueous phases.

A review on solid phase extraction of actinides and lanthanides with amide based extractants.

Solid phase extraction is gaining attention from separation scientists due to its high chromatographic utility. Though both grafted and impregnated forms of solid phase extraction resins are popular, the later is easy to make by impregnating a given organic extractant on to an inert solid support. Solid phase extraction on an impregnated support, also known as extraction chromatography, combines the advantages of liquid-liquid extraction and the ion exchange chromatography methods. On the flip side, the impregnated extraction chromatographic resins are less stable against leaching out of the organic extractant from the pores of the support material. Grafted resins, on the other hand, have a higher stability, which allows their prolong use. The goal of this article is a brief literature review on reported actinide and lanthanide separation methods based on solid phase extractants of both the types, i.e., (i) ligand impregnation on the solid support or (ii) ligand functionalized polymers (chemically bonded resins). Though the literature survey reveals an enormous volume of studies on the extraction chromatographic separation of actinides and lanthanides using several extractants, the focus of the present article is limited to the work carried out with amide based ligands, viz. monoamides, diamides and diglycolamides. The emphasis will be on reported applied experimental results rather than on data pertaining fundamental metal complexation.

Diglycolamide-functionalized poly(propylene imine) diaminobutane dendrimers for sequestration of trivalent f-elements: synthesis, extraction and complexation.

Three diglycolamide-functionalized poly(propylene imine) diaminobutane dendrimers, viz., zero generation (LI), first generation (LII), and second generation (LIII), were synthesized and evaluated for their complexation ability towards trivalent actinides and lanthanides. The distribution coefficient (D) of Am3+ with 1.0 mmol L-1 ligand in 3 M HNO3 follows the order: 0.1 (LI) < 42 (LII) < 110 (LIII). Slope analysis indicated the stoichiometry of the extracted complexes as: 1 : 2 (M : L) for LI and 1 : 2 (M : L) for both LII and LIII. A complexation study of a representative lanthanide (Eu3+) with the three ligands by absorption spectroscopy and luminescence spectroscopy confirmed the formation of the above stoichiometry. The stability constants (log ß) for the ML complexes of Eu3+ with the three ligands were determined to be 5.2 ± 0.03, 5.3 ± 0.01, and 5.4 ± 0.02 for LI, LII, and LIII, respectively. The identical log ß values (within experimental error) for all the ligands indicate that the complexation is not affected by the branching of the ligands. The metal/ligand complex formation was explained with the help of spectroscopic data.

Thermodynamics of biphasic lanthanide extraction by tripodal diglycolamide: a solution calorimetry study.

Isothermal titration calorimetry was employed for the direct measurement of the enthalpy of extraction (ΔHextr) of Eu(NO3)3 by using a tripodal diglycolamide (T-DGA) ligand dissolved in n-dodecane containing 5% (v/v) 2-decanol. The enthalpy of extraction obtained by titration calorimetry was in good agreement with the enthalpy of extraction calculated from the temperature dependence of the distribution coefficients by using the van't Hoff equation. The Gibbs free energy and the entropy of extraction (ΔGextr and ΔSextr) for the extraction of Eu(NO3)3 by T-DGA were also obtained by solvent extraction experiments. The complexation of Eu3+ with T-DGA in a mixture of acetonitrile/nitric acid was also studied by spectrophotometry and calorimetry to determine the stability constants and the enthalpy of complexation (ΔHcomp) for the Eu3+/T-DGA complexes in a single phase. The enthalpy of complexation, though obtained in a solvent different from that in the solvent extraction, allows a rough estimate of the enthalpy of phase transfer of the Eu3+/T-DGA complexes from the aqueous phase to the organic phase.

Complexation of Lanthanides with Glutaroimide-dioxime: Binding Strength and Coordination Modes.

The complexation of lanthanides (Nd(3+) and Eu(3+)) with glutaroimide-dioxime (H2L), a cyclic imide dioxime ligand that has been found to form stable complexes with actinides (UO2(2+) and NpO2(+)) and transition metal ions (Fe(3+), Cu(2+), etc.), was studied by potentiometry, absorption spectrophotometry, luminescence spectroscopy, and microcalorimetry. Lanthanides form three successive complexes, M(HL)(2+), M(HL)L, and M(HL)2(+) (where M stands for Nd(3+)/Eu(3+) and HL(-) stands for the singly deprotonated ligand). The enthalpies of complexation, determined by microcalorimetry, show that the formation of these complexes is exothermic. The stability constants of Ln(3+)/H2L complexes are several orders of magnitude lower than that of the corresponding Fe(3+)/H2L complexes but are comparable with that of UO2(2+)/H2L complexes. A structure of Eu(3+)/H2L complex, identified by single-crystal X-ray diffractometry, shows that the ligand coordinates to Eu(3+) in a tridentate mode, via the two oxygen atoms of the oxime group and the nitrogen atom of the imide group. The relocation of protons of the oxime groups (-CH═N-OH) from the oxygen to the nitrogen atom, and the deprotonation of the imide group (-CH-NH-CH-) result in a conjugated system with delocalized electron density on the ligand (-O-N-C-N-C-N-O-) that forms strong complexes with the lanthanide ions.

Complexation of Neptunium(V) with Glutaroimide Dioxime: A Study by Absorption Spectroscopy, Microcalorimetry, and Density Functional Theory Calculations.

Complexation of NpO2(+) ions with glutaroimide dioxime (H2L), a cyclic imide dioxime ligand that has been shown to form strong complexes with UO2(2+) in aqueous solutions, was studied by absorption spectroscopy and microcalorimetry in 1.0 M NaClO4 aqueous solutions. NpO2(+) forms two successive complexes, NpO2(HL)(aq) and NpO2(HL)2(-) (where HL(-) stands for the partially deprotonated glutaroimide dioxime ligand), with stability constants of log ß111 = 17.8 ± 0.1 and log ß122 = 33.0 ± 0.2, respectively. The complexation is both enthalpy- and entropy-driven, with negative enthalpies (ΔH111 = -52.3 ± 1.0 kJ/mol and ΔH122 = -96.1 ± 1.4 kJ/mol) and positive entropies (ΔS111 = 164 ± 3 J/mol/K and ΔS122 = 310 ± 4 J/mol/K). The thermodynamic parameters suggest that, similar to complexation of UO2(2+), the ligand coordinates with NpO2(+) in a tridentate mode, via the two oxygen atoms of the oxime groups and the nitrogen atom of the imide group. Density functional theory calculations have helped to interpret the optical absorption properties of the NpO2(HL)2(-) complex, by showing that the cis and trans configurations of the complex have very similar energies so that both configurations could be present in the aqueous solutions. It is the noncentrosymmetric cis configuration that makes the 5f → 5f transition allowable so that the NpO2(HL)2(-) complex absorbs in the near-IR region.

A remarkable enhancement in Am³âº/Eu³âº selectivity by an ionic liquid based solvent containing bis-1,2,4-triazinyl pyridine derivatives: DFT validation of experimental results.

Mutual separation of trivalent actinide (An(3+)) and lanthanide (Ln(3+)) using several soft (N) donor ligands (bis(5,6-dialkyl-1,2,4-triazinyl)pyridine (R-BTP)) is attempted for the first time in room temperature ionic liquid (RTIL) medium. The results indicate a spectacular enhancement in the selectivity as compared to that in molecular diluents with a separation factor (S.F.) of >3000 for Am(3+) over Eu(3+) using the methyl derivative (Me-BTP) in RTIL medium using [C(n)mim]·[NTf2] as the diluents (where n = 2, 3, 4, 6 or 8). Such a high S.F. value has never been reported before with any of the R-BTP derivatives in molecular diluents. An opposite trend in the distribution ratio values of both Am(3+) and Eu(3+) with the increasing size of the alkyl (R) group is observed in RTIL medium when compared with that in molecular diluents. The differences in the extraction behaviour of R-BTPs in RTILs vis-à-vis molecular diluents are explained on the basis of the difference in the nature of complexes extracted in these two distinctly different media as supported by the time resolved fluorescence (TRFS) study. An unusually high extractability and selectivity for Am(3+) over Eu(3+) with Me-BTP was attributed to the formation of a 1 : 4 complex for Am(3+), which was never reported earlier with any of the R-BTP derivatives in molecular diluents. DFT studies indicated higher metal 'd' and 'f' orbital participation (covalence) in the bonding with R-BTP in the case of Am(3+) complexes as compared to that in the case of Eu(3+) complexes, which resulted in the selectivity of these classes of ligands. The observed results may have a great significance in the radioactive waste management involving the partitioning and transmutation strategy.

Binding of pyrazine-functionalized calix[4]arene ligands with lanthanides in an ionic liquid: thermodynamics and coordination modes.

The complexation of representative lanthanides with three calix[4]arenes functionalized with four pyrazine pendent arms containing different substituents such as carbamoyl dioctyl (), diisopropyl phosphonate (), and diphenyl phosphoryl () was investigated in water-saturated 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BumimTf2N) by absorption spectroscopy, luminescence spectroscopy, and microcalorimetry. All three ligands form 1 : 1 ML complexes (M = Eu(3+) and L = ligand), and the stability constants (log ß) follow the order: (-1.38 ± 0.66) ≪ (3.71 ± 0.02) < (7.47 ± 0.03), similar to the trend in the metal distribution coefficients in solvent extraction using these ligands as extractants. The enthalpy of complexation, determined by microcalorimetry, shows that the complexation of lanthanides with these bulky ligands is exothermic, and proceeds via replacement of water molecules from the primary coordination spheres. The 1 : 1 stoichiometry of the ML complexes was confirmed by electrospray ionization mass spectrometry. Results from optical absorption, luminescence and (31)P-NMR spectroscopy suggest that, out of four pendent arms on the rigid calixarene platform, only two arms coordinate with the lanthanide ion and each arm is tridentate. The influence of structural features of the ligand on the complexation of lanthanides is explained with the help of thermodynamic parameters.