RESUMO
Ln3+-doped (Ln = lanthanide) nanocrystals are garnering strong interest for their potential as optical materials in various applications. For that reason, a thorough understanding of photophysical processes and ways to tune them in these materials is of great importance. This study, using Eu3+-doped Sr2YF7 as a well-suited model system, underscores the (not unexpected) significance of surface site occupation of Ln3+ and also challenges the prevailing views about their contribution to the luminescence of the system. High-temperature cation exchange and epitaxial shell growth allow nanocrystals to exclusively feature Eu3+ residing at the surface or in the interior, thereby separating their spectral responses. Meticulous experiments reveal that nanocrystals with high doping concentrations exhibit luminescence primarily from surface Eu3+, in contrast to the popular belief that luminescence from surface Ln3+ is largely negligible. The present study shows, on the one hand, the necessity to revise common ideas and also reveals the potential for manipulating the luminescence of such materials through an, until now, unperceived way of surface engineering.
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Employing ionic liquid-assisted microwave synthesis and moderate heat treatment allows for the preparation of otherwise difficult-to-obtain perovskite-type BaSn1-xZrxO3 solid solutions (0 ≤ x ≤ 1). The impact of substituting Sn for the crystal structure, crystallinity, morphology, and photocatalytic performance was investigated. The obtained materials are characterized by X-ray diffraction, scanning electron microscopy, Brunauer-Emmett-Teller (BET) surface area analysis, X-ray photoelectron spectroscopy, UV-Vis diffuse reflectance spectroscopy, photoluminescence spectroscopy, and Raman and IR spectroscopy. SEM images show that the morphology of the samples varies from rods for x = 0, 0.2 to spherical for x = 0.5, 0.8, 1. Upon Zr for Sn substitution, the band gap changes from 3.1 to 5.0 eV as the valence and conduction bands move to lower and higher energies. The photocatalytic activities of the BaSn1-xZrxO3 samples in the hydroxylation of terephthalic acid (TA) follow the order BaSn0.5Zr0.5O3> BaSn0.8Zr0.2O3> BaSnO3> BaSn0.2Zr0.8O3> BaZrO3. The superior photocatalytic activity of BaSn0.5Zr0.5O3 can be attributed to the synergistically favorable combination of a suitable band structure, band gap size, and increased surface area-to-volume ratio, resulting in a diminished crystalline particle size unattainable from samples prepared via traditional synthetic routes or without ionic liquid.
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SrMn2P2 and CaMn2P2 are insulators that adopt the trigonal CaAl2Si2-type structure containing corrugated Mn honeycomb layers. Magnetic susceptibility χ and heat capacity versus temperature T data reveal a weak first-order antiferromagnetic (AFM) transition at the Néel temperature [Formula: see text] K for SrMn2P2 and a strong first-order AFM transition at [Formula: see text] K for CaMn2P2 Both compounds exhibit isotropic and nearly T-independent [Formula: see text], suggesting magnetic structures in which nearest-neighbor moments are aligned at [Formula: see text] to each other. The 31P NMR measurements confirm the strong first-order transition in CaMn2P2 but show critical slowing down above [Formula: see text] for SrMn2P2, thus also evidencing second-order character. The 31P NMR measurements indicate that the AFM structure of CaMn2P2 is commensurate with the lattice whereas that of SrMn2P2 is incommensurate. These first-order AFM transitions are unique among the class of (Ca, Sr, Ba)Mn2 (P, As, Sb, Bi)2 compounds that otherwise exhibit second-order AFM transitions. This result challenges our understanding of the circumstances under which first-order AFM transitions occur.
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A series of 19 ionic liquids (ILs) based on phosphonium and imidazolium cations of varying alkyl-chain lengths with the orthoborate anions bis(oxalato)borate [BOB]- , bis(mandelato)borate, [BMB]- and bis(salicylato)borate, [BScB]- , are synthesized and studied using small-angle neutron scattering (SANS). All measured systems display nanostructuring, with 1-methyl-3-n-alkyl imidazolium-orthoborates forming clearly bicontinuous L3 spongelike phases when the alkyl chains are longer than C6 (hexyl). L3 phases are fitted using the Teubner and Strey model, and diffusely-nanostructured systems are primarily fitted using the Ornstein-Zernicke correlation length model. Strongly-nanostructured systems have a strong dependence on the cation, with molecular architecture variation explored to determine the driving forces for self-assembly. The ability to form well-defined complex phases is effectively extinguished in several ways: methylation of the most acidic imidazolium ring proton, replacing the imidazolium 3-methyl group with a longer hydrocarbon chain, substitution of [BOB]- by [BMB]- , or exchanging the imidazolium for phosphonium systems, irrespective of phosphonium architecture. The results suggest there is only a small window of opportunity, in terms of molecular amphiphilicity and cation:anion volume matching, for the formation of stable extensive bicontinuous domains in pure bulk orthoborate-based ILs. Particularly important for self-assembly processes appear to be the ability to form H-bonding networks, which offer additional versatility in imidazolium systems.
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The new phase Mg7Pt4Ge4 (≡Mg8â¡1Pt4Ge4; â¡ = vacancy) was prepared by reacting a mixture of the corresponding elements at high temperatures. According to single crystal X-ray diffraction data, it adopts a defect variant of the lighter analogue Mg2PtSi (≡Mg8Pt4Si4), reported in the Li2CuAs structure. An ordering of the Mg vacancies results in a stoichiometric phase, Mg7Pt4Ge4. However, the high content of Mg vacancies results in a violation of the 18-valence electron rule, which appears to hold for Mg2PtSi. First principle density functional theory calculations on a hypothetical, vacancy-free "Mg2PtGe" reveal potential electronic instabilities at EF in the band structure and significant occupancy of states with an antibonding character resulting from unfavorable Pt-Ge interactions. These antibonding interactions can be eliminated through introduction of Mg defects, which reduce the valence electron count, leaving the antibonding states empty. Mg itself does not participate in these interactions. Instead, the Mg contribution to the overall bonding comes from electron back-donation from the (Pt, Ge) anionic network to Mg cations. These findings may help to understand how the interplay of structural and electronic factors leads to the "hydrogen pump effect" observed in the closely related Mg3Pt, for which the electronic band structure shows a significant amount of unoccupied bonding states, indicating an electron deficient system.
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The understanding of structure and bonding in intermetallic phases still lags behind that of molecular compounds. For that reason, exploring intermetallic phases and identifying structural patterns and relationships are particularly important for closing this knowledge gap. In particular, here we report on the addition of increasing amounts of platinum to â¼2:1 mixtures of tin and neodymium, which yields eight ternary Pt/Sn/Nd compounds, four of which have not been reported before. Interestingly, except for PtSnNd (1), all observed ternary phases of the system can be derived from the binary compounds Sn2Nd and Sn5Nd2 by adding Pt to the composition(s), as they lie on or close to two lines: Sn2Nd-Pt (Pt0.21(1)Sn2Nd (2), PtSn2Nd (3), Pt1.33Sn2Nd (4), Pt2-xSn2+xNd (x = 0.27(3), 5), and Pt3Sn2Nd (6)) or Sn5Nd2-Pt (Pt1.5Sn5-xNd2 (x = 0.16(2), 7) and Pt3Sn5Nd2-x (x = 0.161(8), 8)). While the introduction of increasing amounts of Pt to the binaries Sn2Nd and Sn5Nd2 leads to stepwise changes in the coordination environment of Nd, Pt preserves its coordination over the entire system in the form of interpenetrating bipyramidal {PtSn5Nd5} clusters.
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A series of four homologous silicides have been discovered during systematic explorations in the central part of the La-Ni-Si system at 1000 °C. All compounds La12.5Ni28.0Si18.3 (n = 3; a = 28.8686(8), c = 4.0737(2) Å, Z = 3), La22.1Ni39.0Si27.8 (n = 4; a = 20.9340(6), c = 4.1245(2) Å, Z = 1), La32.9Ni49.8Si39.3 (n = 5; a = 24.946(1), c = 4.1471(5) Å, Z = 1), and La44.8Ni66.1Si53.4 (n = 6; a = 28.995(5), c = 4.158(1) Å, Z = 1) crystallize in the hexagonal space group P63/m and can be generalized according to Lan(n+1)+xNin(n+5)+ySi(n+1)(n+2)-z with n = 3-6. Their crystal structures are based on AlB2-type building blocks, fused La-centered Ni6Si6 hexagonal prisms, yielding larger oligomeric equilateral domains with the edge size equal to n. The domains extend along the c axis and show checkered ordering of the cationic and anionic parts, while all their atoms are located on mirror planes. Lan(n+1)+xNin(n+5)+ySi(n+1)(n+2)-z can be considered as a mirror series to the La-rich La(n+1)(n+2)Nin(n-1)+2Sin(n+1), where an exchange of the formal cationic and anionic sites, i.e., La and Si, occurs. The La-Ni-Si system is the first system where two such analogous series have been observed.
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The new ternary compounds La15Ni13Bi5 and La9Ni8Sn5 were obtained by arc melting under argon from appropriate amounts of the elements and subsequent annealing at 800 °C for 2 weeks. Single-crystal X-ray diffraction reveals that they represent two new structure types: La15Ni13Bi5 crystallizes in the hexagonal space group P62m [hP33, a = 14.995(3), c = 4.3421(10) Å, V = 845.5(4) Å3, Z = 1] and La9Ni8Sn5 in P63/m [hP88, a = 23.870(15), c = 4.433(3) Å, V = 2187(3) Å3, Z = 4]. The crystal structures of both compounds are characterized by hexagonal honeycomb-based motifs formed by Ni and Sn that extend along the c axis. The building motif with its three-blade wind turbine shape is reminiscent of the organic molecule triptycene and is unprecedented in extended solids. First-principles calculations have been performed in order to analyze the electronic structure and provide insight into chemical bonding. They reveal significant electron transfer from La to Ni and the respective p-element, which supports the formation of the polyanionic Ni-p-element network. DFT calculations suggest paramagnetic-like behavior for both compounds, which was confirmed by magnetic measurements.
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Utilizing an ionic liquid strategy, we report crystal structures of salts of free anionic nucleobases and base pairs previously studied only computationally and in the gas phase. Reaction of tetrabutylammonium ([N4444]+) or tetrabutylphosphonium ([P4444]+) hydroxide with adenine (HAd) and thymine (HThy) led to hydrated salts of deprotonated adenine, [N4444][Ad]·2H2O, and thymine, [P4444][Thy]·2H2O, as well as the double salt cocrystal, [P4444]2[Ad][Thy]·3H2O·2HThy. The cocrystal includes the anionic [Ad-(HThy)] base pair which is a stable formation in the solid state that has previously not even been suggested. It exhibits Watson-Crick connectivity as found in DNA but which is unusual for the free neutral base pairs. The stability of the observed anionic bases and their supramolecular formations and hydrates has also been examined by electronic structure calculations, contributing to more insight into how base pairs can bind when a proton is removed and highlighting mechanisms of stabilization or chemical transformation in the DNA chains.
Assuntos
Adenina/química , Pareamento de Bases , Timina/química , Ânions , Cristalografia , Ligação de Hidrogênio , Modelos Moleculares , Estrutura Molecular , Conformação de Ácido NucleicoRESUMO
Reaction of the elements yielded Ca3Pt4Bi8 and CaPtBi, which are, to the best of our knowledge, the first reported ternary Ca-Pt-Bi compounds. The compounds crystallize isostructural to the Pd analogs Ca3Pd4Bi8 (own structure type) and CaPdBi (TiNiSi structure type), respectively. Employing a multistep temperature treatment allows for the growth of mm-sized single crystals of Ca3Pd4Bi8 and Ca3Pt4Bi8 from a Bi self-flux. Their crystal structures can be visualized as consisting of a three-dimensional extended polyanion [M4Bi8]6- (M = Pd, Pt), composed of interlinked M-Bi chains propagating along the c direction, and Ca2+ cations residing in one-dimensional channels between the chains. First-principles calculations reveal quasi-one-dimensional electronic behavior with reduced effective electron masses along [001]. Bader analysis points to a strong anionic character of the M species (M = Pd, Pt) in Ca3M4Bi8. Thus, it is more appropriate to address the compounds Ca3Pd4Bi8 and Ca3Pt4Bi8 as a palladide and platinide, respectively. Magnetization measurements indicate diamagnetic behavior with no indications for superconductivity down to 2 K. Electrical resistivity data are consistent with metallic behavior and suggest predominant electron-phonon scattering.
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By employing the pyridinium hexafluorophosphate task-specific ionic liquids 1-butyl-4-methylpyridinium hexafluorophosphate ([C4mpyr][PF6]) and 1-ethylpyridinium hexafluorophosphate ([C2pyr][PF6]) as the reaction medium, mineralizer, structure-directing agent, and, in the case of the smaller pyridinium cation, even a structural component, it was possible to obtain five new alkali metal iron phosphates featuring interconnected FeX6 octahedra and PX4 (X = F, O, or OH) tetrahedra. NaFe(PO3F)2 (1) is a dense 3D structure, RbFe(PO3F)(PO2(OH)F)(PO2(OH)2) (2) features 1D strands, (C2pyr)LiFe(PO3F)3(PO2F2)F (3) has 2D layers, and LiFe(PO3F)(PO2F2)F (4) as well as Cs0.75Fe(PO2.75(OH)0.25F)(PO2F2)2 (5) are 3D open frameworks. While in 1-2 as well as in 4 and 5, FeX6 octahedra and PX4 (X = F, O, or OH) tetrahedra alternate, 3 features octahedra dimers, Fe2X11 (X = F, O, or OH). The magnetic behavior of all compounds is governed by antiferromagnetic interactions. Interestingly, 3 exhibits a broad maximum in the temperature dependence of the magnetic susceptibility, characteristic of a low-dimensional magnetic system consistent with the presence of Fe-Fe dimers in its crystal structure.
RESUMO
Many crystalline materials form polymorphs and undergo solid-solid transitions between different forms as a function of temperature or pressure. However, there is still a poor understanding of the mechanism of transformation. Conclusions about the transformation process are typically drawn by comparing the crystal structures before and after the conversion, but gaining detailed mechanistic knowledge is strongly impeded by the generally fast rate of these transitions. When the crystal morphology does not change, it is assumed that crystallinity is maintained throughout the process. Here we report transformation between polymorphs of ZnCl2(1,3-diethylimidazole-2-thione)2 which are sufficiently slow to allow unambiguous assignment of single crystal to single crystal transformation with shape preservation proceeding through an amorphous intermediate phase. This result fundamentally challenges the commonly accepted views of polymorphic phase transition mechanisms.
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Access to lanthanide acetate coordination compounds is challenged by the tendency of lanthanides to coordinate water and the plethora of acetate coordination modes. A straightforward, reproducible synthetic procedure by treating lanthanide chloride hydrates with defined ratios of the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([C2 mim][OAc]) has been developed. This reaction pathway leads to two isostructural crystalline anhydrous coordination complexes, the polymeric [C2 mim]n [{Ln2 (OAc)7 }n ] and the dimeric [C2 mim]2 [Ln2 (OAc)8 ], based on the ion size and the ratio of IL used. A reaction with an IL : Ln-salt ratio of 5 : 1, where Ln=Nd, Sm, and Gd, led exclusively to the polymer, whilst for the heaviest lanthanides (Dy-Lu) the dimer was observed. Reaction with Eu and Tb resulted in a mixture of both polymeric and dimeric forms. When the amount of IL and/or the size of the cation was increased, the reaction led to only the dimeric compound for all the lanthanide series. Crystallographic analyses of the resulting salts revealed three different types of metal-acetate coordination modes where η2 µκ2 is the most represented in both structure types.
RESUMO
Although compound formation between two elements is well studied, thorough investigations make it possible to uncover new binary compounds. A re-examination of the La-Au system revealed three new phases, which were characterized with respect to their structural and electronic properties as well as thermal stability: La7Au3 (Th7Fe3 type, space group P63mc, Pearson code hP20) appears to be metastable. It can be obtained by slow crystallization from a stoichiometric melt. La3Au2 (U3Si2 type, space group P4/mbm, Pearson code tP10) is stable up to 1013 K, where it decomposes peritectically. La3Au4 (Pu3Pd4 type, space group R3Ì , Pearson code hR14) is thermally stable up to at least 1273 K. In addition, the crystal structures of La2Au (anti-PbCl2 type, space group Pnma, Pearson code oP12) and α-LaAu (FeB type, space group Pnma, Pearson code oP8) could be determined by single-crystal X-ray diffraction. The electronic structures and chemical bonding have been evaluated from first principles calculations. They show that all compounds can be viewed as electron-rich, polar intermetallics.
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In the search for new multifunctional materials, particularly for application in solid-state lighting, a set of terbium salicylato (Sal) complexes of general composition [Cat][Tb(Sal)4] with the commonly ionic liquid-forming (IL) cations [Cat] = (2-hydroxyethyl)trimethylammonium (choline) (Chol+), diallyldimethylammonium (DADMA+), 1-ethyl-3-methylimidazolium (C2C1Im+), 1-butyl-3-methylimidazolium (C4C1Im+), 1-ethyl-3-vinylimidazolium (C2Vim+), and tetrabutylphosphonium (P4444+) were synthesized. All Tb compounds exhibit strong green photoluminescence of high color purity by energy transfer from the ligand in comparison with what the analogous La compounds show, and quantum yields can reach up to 63% upon ligand excitation. When excited with an HF generator, the compounds show strong green electroluminescence with the same features of mission. The findings promise a high potential of application as emitter materials in solid-state lighting. As an additional feature, the Tb compounds show a strong response to applied external fields, rendering them multifunctional materials.
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We report two new rare-earth (R) ternary intermetallic compounds-Ho2Ni0.8T1.2 with T = Si and Ge-that correspond to the R5Ni2T3 phase earlier reported to form in Dy-Ni-T and Ho-Ni-T ternary systems. The compounds crystallize in a filled version of the orthorhombic Zr2Ni1-xP-type structure with x = 0.52; their stoichiometry, determined from both single-crystal and powder X-ray diffraction data, is centered on Ho2Ni0.8T1.2 with a narrow solid solubility range for the silicide, while the germanide appears to be a line phase. In addition to R = Dy and Ho, R2Ni0.8T1.2 compounds also form for R = Y and Tb, representing the first examples of rare-earth-based compounds adopting the Zr2Ni1-xP structural prototype. Bulk magnetization data reveal the main transitions of the ferrimagnetic or ferromagnetic type at TC = 38 K for Ho2Ni0.8Si1.2 and TC = 37 K for Ho2Ni0.8Ge1.2, which are followed by subsequent magnetic reordering at lower temperatures. Neutron diffraction shows complex magnetic structures below TC with both ferromagnetic and antiferromagnetic components and magnetic propagation vector κ1 = [0, 0, 0]. Below TN â 24 K (22 K) for the silicide (germanide), an additional antiferromagnetic coupling following an incommensurate magnetic propagation vector κ2 = [κx, 0, 0] appears to coexist with the first magnetic structure.
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Although rare-earth-metal-transition-metal (R/T) phase diagrams have been explored extensively, our recent studies have uncovered new previously nonexistent binary intermetallics. These compounds belong to a narrow region between 70 and 71.4 atom % of the rare-earth metal but represent four different structure types. The binaries Tb7Pd3 and Er17Pd7 are compositionally approaching (less than 1 atom % difference) the previously reported R2.16Pd0.89 (R = Tb and Er), and apparently form by peritectoid transformation, thus, being hard to detect by fast cooling. Tb7Pd3 (1) crystallizes in the Th7Fe3 structure type (hP20, P63mc, a = 9.8846(4) Å, c = 6.2316(3) Å, Z = 2) while Er17Pd7 (2) belongs to the Pr17Co7 type being its second reported representative (cP96, P213, a = 13.365(2) Å, Z = 4). Er17Pd7 (2) is overlapping with the cubic F-centered Er2.11Pd0.89 (3b, Fd3Ì m, a = 13.361(1) Å, Z = 32) with practically identical unit cell parameters but a significantly different structure. Electronic structure calculations confirm that heteroatomic R-T bonding strongly dominates in all structures; T-T bonding interactions are individually strong but do not play a significant role in the total bonding.
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Starting generally with a 4:6:3 molar ratio of Pt, Sn, and R (where R = La-Sm), with or without the application of a NaCl flux, seven ternary compounds were obtained as single crystals. The platinides Pt4Sn6R3 (R = La-Nd) crystallize with the Pt4Ge6Pr3 type of structure (oP52, Pnma, a = 27.6-27.8 Å, b = 4.59-4.64 Å, c = 9.33-9.40 Å). With R = Pr, Pt4Sn6Pr3-x (oP52, Pnma, a = 7.2863(3) Å, b = 4.4909(2) Å, c = 35.114(1) Å) is also obtained, which might be considered a high-temperature polymorph with disorder on the Sn- and Pr-sites. For R = Nd and Sm, a structurally related isostructural series with a slightly different composition Pt3Sn5R2-x (oP52, Cmc21, a = 4.50-4.51 Å, b = 26.14-26.30 Å, c ≈ 7.29 Å) has been observed, together with Pt7Sn9Sm5 (oS42, Amm2, a = 4.3289(5) Å, b = 28.798(4) Å, c = 7.2534(9) Å) under the same conditions. The latter exhibits the rare Zr5Pd9P7-type structure, linking polar intermetallics to metal phosphides, in accord with P7Pd9Zr5≡Pt7Sn9Sm5. All structures may be described in terms of either negative Pt/Sn networks encapsulating positive R atoms, or {PtSnx} clusters (x = 5, 6, or rarely 7) sharing vertices and edges with R in the second coordination sphere and with considerable heterometallic Pt-R bonding contributions.
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A series of anhydrous acetate salts with uranium {[C2C1im][UO2(OAc)3] (1), [C2C2im][UO2(OAc)3] (2), and [C4C1im][UO2(OAc)3] (3)}, lanthanides {[C2C2im]2[La(OAc)5] (4) and [C2C1im]2[Nd(OAc)5] (5)}, and strontium {[C2C1im]n[Sr(OAc)3]n (6)} (where C2C1im = 1-ethyl-3-methylimidazolium, C2C2im = 1,3-diethylimidazolium, C4C1im = 1-butyl-3-methylimidazolium, and OAc = acetate) have been prepared and structurally characterized. Both lanthanides and strontium are common components of the nuclear fuel waste, and their separation from uranium is an important but still challenging task. A new synthetic approach with dialkylimidazolium acetate ionic liquids (ILs) as the solvent has been developed for the direct synthesis of homoleptic acetates from the corresponding hydrates and, unexpectedly, hardly soluble f-element oxides. Although the group of characterized compounds shows perfect structural variability, all actinide and lanthanide metal ions form monomeric complex anions where the metal cation coordinates to five ligands including two oxygen atoms in the case of uranium, as is commonly observed for uranyl compounds. Crystallographic analyses revealed that the complex [UO2(OAc)3]- anions possess rather standard D3h symmetry featuring a hexagonal-bipyramidal coordination environment, while the lanthanide anions [Ln(OAc)5]2- are fully asymmetric and the Ln3+ cations are 10-coordinated in the form of a distorted bicapped tetragonal antiprism. This is the first report of lanthanide ions coordinated in this fashion. For Sr2+, 9-fold coordination through oxygen atoms in the form of a strongly distorted tricapped trigonal prism is observed. The crystallization of anhydrous, homoleptic, anionic acetate complexes from such a large variety of different metal salts appears to be due to the properties of dialkylimidazolium acetate ILs themselves, including enhanced basicity from the high concentration of free anions and their greater affinity for hydrogen-bonding solutes relative to metal cations.
RESUMO
We investigated whether the relatively Lewis basic imidazole-2-thiones could be used to substitute water ligands bound to f-element cations and generate f-element soft donor complexes. Reactions of 1,3-diethylimidazole-2-thione (C2C2ImT) with Nd(NO3)3·6H2O and UO2Cl2·3H2O led to the isolation of the anhydrous thione complexes Nd(NO3)3(C2C2ImT)3 and UO2Cl2(C2C2ImT)2, characterized by single crystal X-ray diffraction. Differences in the strength of metal-thione interactions have been examined by means of the crystal structure analysis and density functional theory (DFT) calculations. The C2C2ImT ligands were found to be affected by both coordination and noncovalent interactions, making it impossible to deconvolute the effects of one from the other. Calculated partial atomic charges indicated greater ligand-to-metal charge transfer in the [UO2]2+ complex, indicative of a stronger interaction. The reactivity of C2C2ImT demonstrates its usefulness in the preparation of f-element soft donor complexes from readily available hydrates that could be useful intermediates for promoting the coordination and studying the effects of soft donor anions.