Smaller Ln Research Articles

Oxygen Migration Pathways in Layered LnBaCo2O6-δ (Ln = La - Y) Perovskites.

Layered LnBaCo2O6-δ perovskites are important mixed ionic-electronic conductors, exhibiting outstanding catalytic properties for the oxygen evolution/reduction reaction. These phases exhibit considerable structural complexity, in particular, near room temperature, where a number of oxygen vacancy ordered superstructures are found. This study uses bond valence site energy calculations to demonstrate the key underlying structural features that favor facile ionic migration. BVSE calculations show that the 1D vacancy ordering for Ln = Sm-Tb could be beneficial at low temperatures as new pathways with reduced barriers emerge. By contrast, the 2D vacancy ordering for Ln = Dy and Y is not beneficial for ionic transport with the basic layered parent material having lower migration barriers. Overall, the key criterion for low migration barriers is an expanded ab plane, supported by Ba, coupled to a small Ln size. Hence, Ln = Y should be the best composition, but this is stymied by the low temperature 2D vacancy ordering and moderate temperature stability. The evolution of the oxygen cycling capability of these materials is also reported.

High-pressure phase behavior of LnHO (Ln = lanthanides): Entropy stabilization of the fluorite structure

In this study, we investigate the phase behavior in LnHO (Ln = Nd, Gd, and Er) at external pressures up to 5 GPa. In contrast to LaHO, we observed a direct phase transformation from the fluorite-type structure to the anti-Fe2P-type structure in all the compounds examined. In the high-pressure anti-Fe2P-type structure above 3 GPa, the H− and O2− anions are coordinated four-fold and five-fold, respectively, as observed in LaHO. The absence of the PbCl2-type structure by chemical pressure (i.e., smaller Ln3+ substitution) is supported by DFT calculations. We further found a tendency for the fluorite-type structure to stabilize toward the higher-pressure side as the Ln ion becomes smaller; in ErHO and GdHO, the fluorite-type structure survives at the secondary phase even at 5 GPa. This suggests that chemical pressure plays a different role in the structural stabilization than physical pressure. The unexpected observation is interpreted in terms of entropy stabilization since, unlike LaHO and NdHO, the fluorite-type ErHO and GdHO compounds are anion disordered.

Systematic Crystallization of NH4Ln(MoO4)2 as a Family of Layered Compounds (Ln = La-Lu and Y), Derivation of Ln2Mo4O15, Crystal Structure, and Photoluminescence.

NH4Ln(MoO4)2 (Ln = La-Lu lanthanide, Y) was crystallized via hydrothermal reaction as a new family of layered materials, from which phase-pure Ln2Mo4O15 was successfully derived via subsequent annealing at 700 °C for the series of Ln elements excluding Ce and Lu. Detailed structure analysis revealed that the ionic size of Ln3+ decisively determined the crystal structure and Mo/Ln coordination for the two families of compounds. NH4Ln(MoO4)2 was analyzed to be orthorhombic (Pbcn space group, no. 60) and monoclinic (P2/c, no. 13) for the larger and smaller Ln3+ of Ln = La-Gd and Ln = Tb-Lu (including Y), respectively, where both the crystal structures have a layered topology featured by the alternative stacking of a [Ln(MoO4)2]- three-tier infinite anionic layer and interlayer NH4+. Four types of crystal structures were found for the Ln2Mo4O15 series, which are monoclinic (P21/a, no. 14) for Ln = La, triclinic (P1̅, no. 2) for Ln = Pr-Sm, triclinic (P1̅, no. 2) for Ln = Eu and Gd, and monoclinic (P21/c, no. 14) for Ln = Tb-Yb (including Y). The photoluminescence of NH4Ln(MoO4)2 (Ln = Eu, Tb) and Ln2Mo4O15:Eu3+ (Ln = La, Gd, Y) was thoroughly investigated in terms of spectral features, quantum efficiency, fluorescence decay, and CIE chromaticity. The thermal stability of luminescence was also studied for Ln2Mo4O15:Eu3+, and the observed charge-transfer excitation components were successfully correlated with the features of the Mo-O polyhedron/unit.

Colon cancer microsatellite instability influences computed tomography assessment of regional lymph node morphology and diagnostic performance

PurposeTo elucidate whether a high level of microsatellite instability (MSI-high) in colon cancer influences the CT assessment of regional lymph node (rLN) morphology and diagnostic performance on predicting pathological node-negative (pN0) patients. MethodWe retrospectively reviewed 507 patients with cecal/proximal ascending colon cancer (age, 63.0 ± 11.6 years; MSI-stable, n = 398; MSI-high, n = 109) who underwent right hemicolectomy between July 1, 2009, and December 31, 2018. Preoperative CT images were assessed for number of rLNs, long/short diameter of the largest rLN, and CT LN grade (CTN0, low probability of metastasis; CTN1, borderline; CTN2, high probability). Sensitivity, specificity, positive predictive value and negative predictive value for predicting pN0 was calculated. Multivariable logistic regression analysis was performed. Statistical significance was defined as P < 0.05. ResultsA study population of 507 patients (mean age ± standard deviation, 63.0 ± 11.6; 264 women) were evaluated. In patients with rLN metastasis, the rLN long axis (pN1: P = 0.013, pN2: P = 0.039) and short axis (pN1: P = 0.001, pN2: P = 0.009) were both longer in MSI-high tumors compared with MSI-stable tumors. High specificity for predicting pN0 was only achieved in MSI-high tumors [sensitivityMSI-stable = 58.3% (n = 137/235), specificityMSI-stable = 71.2% (n = 116/163); sensitivityMSI-high = 38.4% (n = 33/86), specificityMSI-high = 91.3% (n = 21/23)]. Multivariable logistic regression indicated MSI-high (P < 0.001, odds ratio = 3.701), smaller LN long axis (P = 0.023, odds ratio = 0.905), and lower CT LN grade (CTN0: P = 0.009, odds ratio = 2.987; CTN1: P = 0.014, odds ratio = 2.195) as significant parameters in predicting pN0. ConclusionMSI-high colon cancer is associated with larger rLNs and high specificity for predicting pN0 on CT assessment.

Modelling the spectra of the kilonova AT2017gfo – I. The photospheric epochs

ABSTRACT The kilonova (KN) associated with the binary neutron star (BNS) merger GW170817 is the only known electromagnetic counterpart to a gravitational wave source. Here we produce a sequence of radiative transfer models (using tardis) with updated atomic data, and compare them to accurately calibrated spectra. We use element compositions from nuclear network calculations based on a realistic hydrodynamical simulation of a BNS merger. We show that the blue spectrum at +1.4 d after merger requires a nucleosynthetic trajectory with a high electron fraction. Our best-fitting model is composed entirely of first r-process peak elements (Sr and Zr) and the strong absorption feature is reproduced well by Sr ii absorption. At this epoch, we set an upper limit on the lanthanide mass fraction of $X_{{\small LN}} \lesssim 5 \times 10^{-3}$. In contrast, all subsequent spectra from +2.4 to 6.4 d require the presence of a modest amount of lanthanide material ($X_{{\small LN}} \simeq 0.05^{+0.05}_{-0.02}$), produced by a trajectory with Ye = 0.29. This produces lanthanide-induced line blanketing below 6000 Å, and sufficient light r-process elements to explain the persistent strong feature at ∼0.7–1.0 $\mu$m (Sr ii). The composition gives good matches to the observed data, indicating that the strong blue flux deficit results in the near-infrared (NIR) excess. The disjoint in composition between the first epoch and all others indicates either ejecta stratification, or the presence of two distinct components of material. This further supports the ‘two-component’ KN model, and constrains the element composition from nucleosynthetic trajectories. The major uncertainties lie in availability of atomic data and the ionization state of the expanding material.

Liquid crystalline behavior and photoluminescence of lanthanide decanoate nanoparticles synthesized by microwave radiation.

Luminescent lanthanide decanoate nanoparticles (LnC10 NPs; Ln = Pr, Nd, Sm, Eu, Gd, Er) with spherical morphology (<100 nm) have been synthesized via a facile microwave (MWV) method using Ln(NO3)3·xH2O, ethanol/water, and decanoic acid. These hybrid nanomaterials adopt a lamellar structure consisting of inorganic Ln3+ layers separated by a decanoate anion bilayer and exhibit liquid crystalline (LC) phases during melting. The particle size, crystalline structure, and LC behavior were characterized using transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and powder X-ray diffraction (ambient and heated). Thermal analysis indicated the formation of Smectic A LC phases by LnC10 nanoparticles, with the smaller lanthanides (Ln = Sm, Gd, Er) displaying additional solid intermediate and Smectic C phases. The formation of LC phases by the smaller Ln3+ suggests that these nanoscale materials have vastly different thermal properties than their bulk counterparts, which do not exhibit LC behavior. Photoluminescence spectroscopy revealed the LnC10 NPs to be highly optically active, producing strong visible emissions that corresponded to expected electronic transitions by the various Ln3+ ions. Under long-wave UV irradiation (λ = 365 nm), bright visible luminescence was observed for colloidal suspensions of Nd, Sm, Eu, Gd, and ErC10 NPs. To the best of the authors' knowledge, this is the first reported synthesis of nanoscale metal alkanoates, the first report of liquid crystalline behavior by any decanoate of lanthanides smaller than Nd, and the first observation of strong visible luminescence by non-vitrified lanthanide alkanoates.

Generalized synthesis of NaLn(MoO4)2 nano/microcrystals (Ln = La–Lu and Y): The effects of lanthanide contraction, structure, and down-/up-conversion luminescence

Systematic synthesis of scheelite-type double molybdate nano-/microcrystals NaLn (MoO4)2 (Ln = La–Lu lanthanides and Y) was successfully carried out via hydrothermal reaction at 180 °C without using any organic additive, and the intrinsic effects of lanthanide contraction on phase preference and crystallite morphology were unambiguously observed. It was shown that the products of larger Ln3+ (Ln = La–Dy) and smaller Ln3+ (Ln = Ho–Lu and Y) elements crystallized as tetragonal NaLn (MoO4)2 and new orthorhombic NaLnMo2O8·2H2O structures, respectively, with the latter being able to dehydrate to tetragonal NaLn (MoO4)2 upon calcination at ∼300 °C. Y was found to be a demarcation point for the two structures, and phase preference was shown to be influenced by solution pH and MoO42−/Y3+ molar ratio. With Eu3+ as a downconversion (DC) luminescence probe, the effects of Ln type (Ln = La, Gd, Y and Lu) and crystal structure were manifested. Furthermore, the upconversion (UC) luminescence of Yb3+/Ho3+ and Yb3+/Er3+ pairs in NaLu(MoO4)2 was studied for the first time, and strong red and green UC emissions were observed under the 978 nm laser excitation. Besides, the processes/mechanisms of UC were studied via varying the excitation power and were discussed with Yb3+-MoO42- dimer sensitizer.

Intralanthanide Separation on Layered Titanium(IV) Organophosphate Materials via a Selective Transmetalation Process.

The lanthanides (Ln) are an essential part of many advanced technologies. Our societal transformation toward renewable energy drives their ever-growing demand. The similar chemical properties of the Ln pose fundamental difficulties in separating them from each other, yet high purity elements are crucial for specific applications. Here, we propose an intralanthanide separation method utilizing a group of titanium(IV) butyl phosphate coordination polymers as solid-phase extractants. These materials are characterized, and they contain layered structures directed by the hydrophobic interaction of the alkyl chains. The selective Ln uptake results from the transmetalation reaction (framework metal cation exchange), where the titanium(IV) serves as sacrificial coordination centers. The “tetrad effect” is observed from a dilute Ln3+ mixture. However, smaller Ln3+ ions are preferentially extracted in competitive binary separation models between adjacent Ln pairs. The intralanthanide ion-exchange selectivity arises synergistically from the coordination and steric strain preferences, both of which follow the reversed Ln contraction order. A one-step aqueous separation of neodymium (Nd) and dysprosium (Dy) is quantitatively achievable by simply controlling the solution pH in a batch mode, translating into a separation factor of greater than 2000 and 99.1% molar purity of Dy in the solid phase. Coordination polymers provide a versatile platform for further exploring selective Ln separation processes via the transmetalation process.

(OA29) Low Rate of Contralateral Neck Failure in T1-2N2B TONSIL PATIENTS Treated With Ipsilateral Neck Radiation

Treatment of advanced oropharyngeal carcinomas generally entails bilateral radiation therapy. However, multiple single institutional retrospective studies have demonstrated low rates of contralateral neck failure in patients treated with radiation to the primary tumor and ipsilateral neck for well-lateralized tonsil cancer with N0-N2a (up to 1 lymph node, LN) disease. Avoidance of the contralateral neck results in both decreased acute and long-term side effects from treatment, however this reduction in radiation field must be balanced against the possibility of increased local recurrence There is little data specifically examining the possibility of omission of contralateral neck radiation in tonsil patients with N2b disease (>1 small LN). The purpose of our study is to review the institutional experiences at The University of Cincinnati and the University of Texas, MD Anderson Cancer Center in treating patients specifically with T1-T2N2b squamous cell carcinoma of the tonsil with ipsilateral neck irradiation to evaluate the rates of contralateral neck failure and assess treatment-related toxicities. We retrospectively reviewed the records of patients with squamous cell carcinoma of the tonsil who received definitive radiation between 1999 and 2017 at The MD Anderson Cancer Center and The University of Cincinnati. A total of 86 patients with T1-T2N2b were included and all other T and N stages were excluded. Of the 86 patients, 57 patients were p16+, 2 were p16 negative, and 27 had unknown p16 status. The rate of contralateral neck failure was determined. Radiation-related acute and late toxicities were documented. Of the 86 patients treated with ipsilateral radiation, 2 patients failed in the contralateral neck, for an absolute contralateral neck failure rate of 2.5%. One patient failed in the contralateral neck 3.6 months after treatment and the other patient failed in the contralateral neck at 21.1 months. There were no other contralateral failures after 21.1 months. The median follow-up was 78.7 months (range 3.4 – 205 months). Both of the contralateral neck failures were successfully salvaged. One patient underwent a salvage neck dissection followed by adjuvant ipsilateral neck radiotherapy and the other was salvaged with contralateral neck radiation. There were two patients with disease recurrence within the treatment field; one patient had persistent disease at the end of treatment and the second patient was found to have an in-field recurrence at 9 months. 33% received concurrent chemotherapy and 15% received induction chemotherapy. 7% required a feeding tube at the end of treatment. The contralateral neck failure rate in T1-T2N2b tonsil patients treated with ipsilateral neck RT is low. Feeding tube requirement is also low compared to historical controls from randomized trials (ranging from 15-50%). Moreover, both of the patients in our study who recurred within the contralateral neck were successfully salvaged. As multiple ongoing studies attempt to de-escalate treatment in the HPV+ oropharyngeal cancer population to reduce morbidities of treatment, our data supports decreasing the treatment volume in an effort to minimize toxicity. Ipsilateral neck irradiation should be considered in patients with well-lateralized T1-T2N2b tonsillar cancer, particularly those that are HPV+.

Effect of the lanthanoid-size on the structure of a series of lanthanoid-anilato 2-D lattices

We report the synthesis and characterization of a series of Ln-based bromoanilato 2-D lattices with dimethyl sulfoxide (DMSO): [Ln2(C6O4Br2)3(DMSO)n]·2DMSO·mH2O with n = 6 and m = 0 for Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6) and Gd (7); n = 4 and m = 2 for Ln = Tb (8), Dy (9), Ho (10), Er (11), Tm (12) and Yb (13) (C6O4Br22− = 3,6-dibromo-2,5-dihydroxy-1,4-benzoquinone = bromoanilato). The X-ray analysis shows that the largest Ln(III) ions (La-Gd, 1-7) crystallize in the monoclinic P21/n space group (phase I), whereas the smaller Ln(III) ions (Tb–Yb, 8–13) crystallize in the triclinic P-1 space group (phase II). Both phases present a (6,3)-2-D topology but show important differences derived from the different coordination number of the Ln(III) in both phases. In phase I, the Ln(III) ions are nine-coordinate with a tri-capped trigonal prism geometry and rectangular cavities with no solvent molecules. In phase II, the Ln(III) ions are eight-coordinate with a triangular dodecahedral geometry and distorted hexagonal cavities having two water molecules. These differences are due to the lanthanoid contraction. The magnetic properties show that the Ln(III) ions are isolated and do not present any noticeable magnetic interactions as expected for bromoanilato bridges and Ln(III) ions.

Complete and limited substitution of rare-earth elements in apatite silicates La(9-x)Lnx(SiO4)6O1.5

The isomorphous substitution of smaller RE elements (Ln = Nd, Eu, Gd, Ho, Tm, and Yb) for lanthanum in the apatite silicate solid solutions La9−xLnx(SiO4)6O1.5 was studied by X-ray powder diffraction and the Rietveld structure refinement, scanning electron microscopy and energy-dispersive X-ray microanalysis. Single-phase samples were prepared by solid-state synthesis at a moderate temperature of 1200 °C using an amorphous SiO2 nanopowder (10–40 nm) as a reactant. As the atomic number of Ln increases, the complete solubility, 0 ≤ x ≤ 9, found in the systems with Ln = Nd, Eu, Gd, and Ho changes to a limited one for Ln = Tm (0 ≤ x < 1.5) and Yb (0 ≤ x < 1). The distribution of La and smaller Ln over two structurally independent cationic sites is close to statistical. In both cationic polyhedra, Ln(1)O9 and Ln(2)O7, the bond lengths Ln – O decrease with x, except the longest bonds Ln(1) – O(3) and Ln(2) – O(1) which increase slightly. The experimental results on the substitution limits agree with the values of the mixing energy, and critical temperature of miscibility calculated in the approximation of a regular solid solution.

Lanthanide stannate pyrochlores (Ln2Sn2O7; Ln = Nd, Gd, Er) at high pressure

Lanthanide stannate pyrochlores (Ln2Sn2O7; Ln = Nd, Gd, and Er) were investigated in situ to 50 GPa in order to determine their structural response to compression and compare their response to that of lanthanide titanate, zirconate, and hafnate pyrochlores. The cation radius ratio of A3+/B4+ in pyrochlore oxides (A2B2O7) is thought to be the dominant feature that influences their response on compression. The ionic radius of Sn4+ is intermediate to that of Ti4+, Zr4+, and Hf4+, but the 〈Sn–O〉 bond in stannate pyrochlore is more covalent than the 〈B–O〉 bonds in titanates, zirconate, and hafnates. In stannates, based on in situ Raman spectroscopy, pyrochlore cation and anion sublattices begin to disorder with the onset of compression, first measured at 0.3 GPa. The extent of sublattice disorder versus pressure is greater in stannates with a smaller Ln3+ cation. Stannate pyrochlores (Fd-3m) begin a sluggish transformation to an orthorhombic, cotunnite-like structure at ~28 GPa; similar transitions have been observed in titanate, zirconate, and hafnate pyrochlores at varying pressures (18–40 GPa) with cation radius ratio. The extent of the phase transition versus pressure varies directly with the size of the Ln3+ cation. Post-decompression from ~50 GPa, Er2Sn2O7 and Gd2Sn2O7 adopt a pyrochlore structure, rather than the multi-scale defect-fluorite + weberite-type structure adopted by Nd2Sn2O7 that is characteristic of titanate, zirconate, and hafnate pyrochlores under similar conditions. Like pyrochlore titanates, zirconates, and hafnates, the bulk modulus, B0, of stannates varies linearly and inversely with cation radius ratio from 1 1 1 GPa (Nd2Sn2O7) to 251 GPa (Er2Sn2O7). The trends of bulk moduli in stannates in this study are in excellent agreement with previous experimental studies on stannates and suggest that the size of the Ln3+ cation is the primary determining factor of B0. Additionally, when normalized to rA/rB, the bulk moduli of stannates are comparable to those of zirconates and hafnates, which vary from titanates. Our results suggest that the cation radius ratio strongly influences the bulk moduli of stannates, as well as their overall compression response.

Facile hydrothermal crystallization of NaLn(WO4)2 (Ln=La-Lu, and Y), phase/morphology evolution, and photoluminescence

Hydrothermal reaction of Ln nitrate and Na2WO4 at pH=8 and 200 °C for 24 hours, in the absence of any additive, has directly produced the scheelite-type sodium lanthanide tungstate of NaLn(WO4)2 for the larger Ln3+ of Ln=La-Dy (including Y, Group I) and an unknown compound that can be transformed into NaLn(WO4)2 by calcination at the low temperature of 600 °C for the smaller Ln3+ of Ln=Ho-Lu (Group II). With the successful synthesis of NaLn(WO4)2 for the full spectrum of Ln, the effects of lanthanide contraction on the structural features, crystal morphology, and IR responses of the compounds were clarified. The temperature- and time-course phase/morphology evolutions and the phase conversion upon calcination were thoroughly studied for the Group I and Group II compounds with Ln=La and Lu for example, respectively. Unknown intermediates were characterized by elemental analysis, IR absorption, thermogravimetry, and differential scanning calorimetry to better understand their chemical composition and coordination. The photoluminescence properties of NaEu(WO4)2 and NaTb(WO4)2, including excitation, emission, fluorescence decay, and quantum efficiency of luminescence, were also comparatively studied for the as-synthesized and calcination products.

Putting ScTGa5(T = Fe, Co, Ni) on the Map: How Electron Counts and Chemical Pressure Shape the Stability Range of the HoCoGa5Type

We explore the factors stabilizing one member of the diverse structures encountered in Ln–T–E systems (Ln = lanthanide or similar early d-block element, T = transition metal, E = p-block element): the HoCoGa5 type, an arrangement of atoms associated with unconventional superconductivity. We first probe the boundaries of its stability range through the growth and characterization of ScTGa5 crystals (T = Fe, Co, Ni). After confirming that these compounds adopt the HoCoGa5 type, we analyze their electronic structure using density functional theory (DFT) and DFT-calibrated Hückel calculations. The observed valence electron count range of the HoCoGa5 type is explained in terms of the 18-n rule, with n = 6 for the Ln atoms and n = 2 for the T sites. The role of atomic sizes is investigated with DFT-chemical pressure (DFT-CP) analysis of ScNiGa5, which reveals negative pressures within the Ga sublattice as it stretches to accommodate the Sc and T atoms. This CP scheme is consistent with HoCoGa5-type gallides only being observed for relatively small Ln and T atoms. These conclusions account for the relative positions of the HoCoGa5, BaMg4Si3, and Ce2NiGa10 types in a structure map, demonstrating how combining the 18-n and CP schemes can guide our understanding of Ln–T–E systems.

Complexation of Ln(3+) Ions with Cyclam Dipicolinates: A Small Bridge that Makes Huge Differences in Structure, Equilibrium, and Kinetic Properties.

The coordination properties toward the lanthanide ions of two macrocyclic ligands based on a cyclam platform containing picolinate pendant arms have been investigated. The synthesis of the ligands was achieved by using the well-known bis-aminal chemistry. One of the cyclam derivatives (cb-tedpa(2-)) is reinforced with a cross-bridge unit, which results in exceptionally inert [Ln(cb-tedpa)](+) complexes. The X-ray structures of the [La(cb-tedpa)Cl], [Gd(cb-tedpa)](+), and [Lu(Me2tedpa)](+) complexes indicate octadentate binding of the ligands to the metal ions. The analysis of the Yb(3+)-induced shifts in [Yb(Me2tedpa)](+) indicates that this complex presents a solution structure very similar to that observed in the solid state for the Lu(3+) analogue. The X-ray structures of [La(H2Me2tedpa)2](3+) and [Yb(H2Me2tedpa)2](3+) complexes confirm the exocyclic coordination of the metal ions, which gives rise to coordination polymers with the metal coordination environment being fulfilled by oxygen atoms of the picolinate groups and water molecules. The X-ray structure of [Gd(Hcb-tedpa)2](+) also indicates exocyclic coordination that in this case results in a discrete structure with an eight-coordinated metal ion. The nonreinforced complexes [Ln(Me2tedpa)](+) were prepared and isolated as chloride salts in nonaqueous media. However, these complexes were found to undergo dissociation in aqueous solution, except in the case of the complexes with the smallest Ln(3+) ions (Ln(3+) = Yb(3+) and Lu(3+)). A DFT investigation shows that the increased stability of the [Ln(Me2tedpa)](+) complexes in solution across the lanthanide series is the result of an increased binding energy of the ligand due to the increased charge density of the Ln(3+) ion.

Key Role of Size and Electronic Configuration on the Sign and Strength of the Magnetic Coupling in a Series of Cu2Ln Trimers (Ln = Ce, Gd, Tb, Dy and Er)

Five new trinuclear complexes with formula [(CuLα−Me)2Ce(NO3)3] (1) and [(CuLα−Me)2Ln(H2O)(NO3)2](NO3)·2(CH3OH) (Ln = Gd(2), Tb(3), Dy(4) and Er(5)) have been synthesized using the bidentate N2O2 donor metalloligand [CuLα−Me] (H2Lα−Me = N,N′-bis(α-methylsalicylidene)-1,3-propanediamine) and structurally characterized. In the case of compound 1, the larger ionic radius of Ce(III) leads to a neutral trinuclear complex with an asymmetric CeO10 tetradecahedron coordination geometry formed by four oxygen atoms from two (CuLα−Me) units and three bidentate NO3− ligands. In contrast, the isomorphic complexes 2–5, with smaller Ln(III) ions, give rise to monocationic trinuclear complexes with a non-coordinated nitrate as a counter ion. In these complexes, the Ln(III) ions show a LnO9 tricapped trigonal prismatic coordination geometry with C2 symmetry formed by four oxygen atoms from two (CuLα−Me) units, two bidentate NO3− ligands and a water molecule. The magnetic properties show the presence of weak antiferromagnetic interactions in 1 and weak ferromagnetic interactions in 2–5. The fit of the magnetic properties of compounds 2–5 to a simple isotropic-exchange symmetric trimer model, including the anisotropy of the Ln(III) ions, shows that in all cases the Cu-Ln magnetic coupling is weak (JCu-Ln = 1.81, 1.27, 0.88 and 0.31 cm−1 for 2–5, respectively) and linearly decreases as the number of unpaired f electrons of the Ln(III) decreases. The value found in compound 2 nicely fits with the previously established correlation between the dihedral Cu–O–O–Gd angle and the J value.

Lanthanide(III) complexation with an amide derived pyridinophane.

Herein we report a detailed investigation of the solid state and solution structures of lanthanide(III) complexes with the 18-membered pyridinophane ligand containing acetamide pendant arms TPPTAM (TPPTAM = 2,2',2″-(3,7,11-triaza-1,5,9(2,6)-tripyridinacyclododecaphane-3,7,11-triyl)triacetamide). The ligand crystallizes in the form of a clathrated hydrate, where the clathrated water molecule establishes hydrogen-bonding interactions with the amide NH groups and two N atoms of the macrocycle. The X-ray structures of 13 different Ln(3+) complexes obtained as the nitrate salts (Ln(3+) = La(3+)-Yb(3+), except Pm(3+)) have been determined. Additionally, the X-ray structure of the La(3+) complex obtained as the triflate salt was also obtained. In all cases the ligand provides 9-fold coordination to the Ln(3+) ion, ten coordination being completed by an oxygen atom of a coordinated water molecule or a nitrate or triflate anion. The bond distances of the metal coordination environment show a quadratic change along the lanthanide series, as expected for isostructural series of Ln(3+) complexes. Luminescence lifetime measurements obtained from solutions of the Eu(3+) and Tb(3+) complexes in H2O and D2O point to the presence of a water molecule coordinated to the metal ion in aqueous solutions. The analysis of the Ln(3+)-induced paramagnetic shifts indicates that the complexes are ten-coordinated throughout the lanthanide series from Ce(3+) to Yb(3+), and that the solution structure is very similar to the structures observed in the solid state. The complexes of the light Ln(3+) ions are fluxional due to a fast Δ(λλλλλλ) ↔ Λ(δδδδδδ) interconversion that involves the inversion of the macrocyclic ligand and the rotation of the acetamide pendant arms. The complexes of the small Ln(3+) ions are considerably more rigid, the activation free energy determined from VT (1)H NMR for the Lu(3+) complex being ΔG(⧧)298 = 72.4 ± 5.1 kJ mol(-1).

Crystal Structure Stabilization of Gadolinium Aluminum Garnet (Gd&lt;sub&gt;3&lt;/sub&gt;Al&lt;sub&gt;5&lt;/sub&gt;O&lt;sub&gt;12&lt;/sub&gt;) and Photoluminescence Properties

To suppress the thermal decomposition and to stabilize the crystal structure of Gd3Al5O12 (GdAG) garnet, doping GdAG with smaller Ln3+ (Ln=Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y, respectively) to form (Gd,Ln)AG solid solutions was proposed in work. Carbonate precursors of (Gd,Ln)AG with an approximate composition of (NH4)x(Gd,Ln)3Al5(OH)y(CO3)z•nH2O were synthesized via coprecipitation from a mixed solution of ammonium aluminum sulfate and rare earth nitrate, using ammonium hydrogen carbonate as the precipitant. The precursors and the calcination derived oxides were characterized using FT-IR spectroscopy, DTA/TG, XRD, BET and FE-SEM. The results showed that smaller Ln3+ doping can indeed stabilize GdAG against its thermal decomposition to a mixture of GdAlO3 (GdAP) and Al2O3 phases at elevated temperatures and at the same time effectively lowers the temperature for garnet crystallization. The carbonate precursors are loosely agglomerated and the resultant (Gd,Ln)AG powders show good dispersion and a fairly uniform particle morphology. The (Gd,Ln)AG solid solutions exhibit decreasing lattice parameters along with decreasing radius of the dopant ions at the same dopant content of 50 at%. Photoluminescence properties of some of the garnet solid solutions are also studied. The materials developed herein may potentially be used for photoluminescent and scintillation applications.

On structure and bonding of lanthanoid trifluorides LnF3 (Ln = La to Lu)

The trends in the series of lanthanoid (lanthanide) trifluoride molecules LnF3 (Ln = La to Lu) are governed by the valence-active Ln(4f,5d,5p,6s) shells. The series is investigated by quasi-relativistic density functional theory at both the scalar and spin-orbit-coupled levels. Integrating many of the previous experimental and theoretical deductions, we obtain the following comprehensive picture: (1) The comparatively small Ln-F bond length contraction of 14 pm from La to Lu is rather smooth but weakly modulated by spin-orbit coupling. (2) From La to Lu the floppy structure becomes more quasi-planar. (3) The heterolytic LnF bond energies (⅓LnF3→⅓Ln(3+) + F(-)) at the spin-orbit averaged level increase smoothly from 15.3 to 16.3 eV for La to Lu, only the 'divalent' lanthanoids Eu and Yb are outliers with 0.2 eV higher bond energies. (4) The homolytic LnF bond energies (⅓LnF3→⅓Ln + F) however show an overall W-shaped double-periodicity with maxima for LaF3, GdF3 and LuF3, decreasing from La to Eu and from Gd to Yb, the large individual variations being caused by different spin-orbit coupling and Coulomb interaction effects in Ln(0) and LnF3. (5) The Ln-F interaction is basically ionic (increasing with decreasing ionic radii) with some dative Ln(3+)← F(-) bonding. (6) The latter is of the Ln(5d)-F(2p) type with a rather constant bond order from La to Lu, with small Ln(5p) and very small Ln(4f) semi-core contributions decreasing from La to Lu. All these trends are rationalized.

Hydrated Rare Earth Structural Networks containing the Phenylene‐1, 2‐dioxydiacetate (PDDA) Ligand

AbstractReaction of LnCl3 with Na2(PDDA) (PDDA = phenylene‐1, 2‐dioxydiacetate) in a 1 to 2 mol ratio in aqueous solution yielded [Ln2(PDDA)3(H2O)6]·2H2O, structurally characterized for Ln = Ce (1), Sm (2) (redetermination), Tb (3) and Y (4) in a monoclinic C2/c array, a second related structural form [orthorhombic, Pbcn] being obtained for Tb (5), Ho (6) and Er (7). The ‘domains of existence' of these two previously described forms are now extended to Ce–Dy, Y, and Eu–Er, respectively. Reaction under the same conditions for the heavier Yb3+ ion yielded [Yb2(PDDA)3(H2O)6](∞|∞)·4H2O (8), orthorhombic, Pbca. In the case of Ln = La the bimetallic species [NaLa(PDDA)2(H2O)2](∞|∞)·4H2O (9) was obtained, while reaction of LnCl3 with Na2(PDDA) in a 1 to 3 mol ratio led to the isolation of the isotypic (monoclinic, P21/c) [NaLn(PDDA)2(H2O)2](∞|∞)·4H2O) for Ln = Ce (10) and Sm (12). With the smaller Ln = Yb, the more definitively bimetallic [NaYb(PDDA)2(H2O)2](∞|∞)·3H2O (13) (triclinic, P$\bar{1}$)) was obtained, the trihydrate solvation ascribed differing from that recorded (dihydrate) in a cosynchronous report.