Rare Earth Complexes with Carboxylic Acids, Polyaminopolycarboxylic Acids, and Amino Acids

Wang, Ruiyao; Zheng, Zhiping

doi:10.1002/9780470824870.ch3

Cited by 13 publications

(5 citation statements)

References 116 publications

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“…To prepare the novel cerium propionate-based coordination polymer, we have applied a well-known synthetic approach based on the ion exchange between RE nitrates and soluble metal carboxylates. − Namely, the interaction of Ce(NO 3 ) 3 with NaProp in a weakly acidic (pH ∼ 5) aqueous solution reproducibly yielded the desired product with no admixtures (e.g., NaNO 3 ) present. To provide the highest purity of the solid product, the evaporation of the solution was stopped early, thus leading to a low yield; however, one could continue the evaporation further to obtain larger amounts of cerium propionate.…”

Section: Resultsmentioning

confidence: 99%

Polytypism and Packing-Dependent Colossal Positive and Negative Thermal Expansion in a 2D Layered Cerium-Based Coordination Polymer

Kendin,

Shaulskaya,

Tsymbarenko

2024

Crystal Growth & Design

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A two-dimensional layered coordination polymer [Ce 2 (H 2 O) 2 Prop 6 ] ∞ (Prop − = C 2 H 5 COO − ) has been crystallized in the form of two polytypes (α and β). Their structural features have been studied by means of variable-temperature single-crystal (VT-SCXRD) and powder (VT-PXRD) X-ray diffraction along with pair distribution function analysis of total X-ray scattering data (PDF). As revealed from VT-SCXRD and PDF data, α and β polytypes possess a similar local structure of layers but differ in the arrangement of layers. Single crystals and powders of [Ce 2 (H 2 O) 2 Prop 6 ] ∞ exhibit highly anisotropic thermal expansion, which is packing-dependent and drastically differs for α and β polytypes. Unit cell parameters for α demonstrate a nonlinear temperature dependence with colossal positive (α 3 CTE = +899 MK −1 ) and negative (α 1 CTE = −427 MK −1 ) linear coefficients of thermal expansion (CTEs) in the 190−210 K range. The temperature dependence of unit cell parameters for β demonstrates no colossal CTEs in the 100−300 K range. Periodic DFT-D calculations have shown the weakening of interlayer interactions (cohesive energies for α and β are 149 and 144 mJ/m 2 at 100 K, and 111 and 129 mJ/m 2 at 300 K, respectively) and relaxation of stressed layers upon heating.

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Section: Resultsmentioning

confidence: 99%

Polytypism and Packing-Dependent Colossal Positive and Negative Thermal Expansion in a 2D Layered Cerium-Based Coordination Polymer

Kendin,

Shaulskaya,

Tsymbarenko

2024

Crystal Growth & Design

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“…1 13 C NMR signals of the carboxylate carbon (C 1 ) when closely and carefully noticed show minute splitting which is clearly seen in the expanded spectrum, while the ethylenic CH 2 carbon (C 2 ) and acetate CH 2 carbon (C 3 …”

Section: H and 13 C Nmr Studiesmentioning

confidence: 95%

“…Rare earth metal-edta chelates were found to possess effective biological activities and interesting structures. [1][2][3][4] Despite several sodium, potassium, and ammonium complexes of lanthanides with amino acids have been investigated, [5][6][7][8][9] the structural studies on hydrazinium complexes are scarce in the literature. Hydrazinium cation, N 2 H 5 + is one of a few positively charged ligands that can play a duel role to satisfy both the primary and secondary valencies of the metal ions.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, Antioxidant, and Antiviral Studies on N₂H₅[Ln(edta)(H₂O)₃].5H₂O (Ln = Pr, Nd, and Sm)

Ragul¹,

Sivasankar²

2013

Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-

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3 ].5H 2 O (Ln = Pr, Nd and Sm) have been prepared and the molecular structures of these crystals were determined by X-ray single crystal study. The Xray powder diffraction patterns of the three complexes reveal that they are isomorphous. These complexes are nine coordinated with a hexadentate edta 4− ion and three coordinated water molecules. However, the remaining five more water molecules present as lattice water. Hydrazinium cation, though capable of coordination with the metal ion, in the present case present outside the coordination sphere as primary valency. The Ln (III)N 2 O 4 O 3 parts in the complex anions have the same structures in all the three complexes. The crystals of Pr(III), Nd(III), and Sm(III) complexes belong to the orthorhombic crystal system and Fdd2 space group. The crystal data are as follows: Pr(III): a = 19.6712(5) Å, b = 35.6939(9) Å, c = 12.3079(4) Å, α = β = γ = 90 • , V = 8641.9(4) Å 3 , R = 0.0255, and Rw = 0.0728 for I>2σ (I) and 10119 reflections. Nd(III): a = 19.6414(3) Å, b = 35.6177(5) Å, c = 12.3212(2) Å, α = β = γ = 90 • , V = 8619.7(2) Å 3 , R = 0.0251, and Rw = 0.0693 for I > 2σ (I) and 7378 reflections. Sm(III): a = 19.5814(3) Å, b = 35.4617(7) Å, c = 12.2931(2) Å, α = β = γ = 90 • , V = 8536.2(3) Å 3 , R = 0.0233, and Rw = 0.0641 for I > 2σ (I) and 6766 reflections. These complexes show promising antioxidant activity as expected for lanthanide(III) ions with unpaired electrons.The antiviral screening also shows enhanced activities of these complexes than the respective non-hydrazinium and ammonium chelates. The crystals of the complexes in purest form were powdered and subjected to constant temperature degradation at 600 • C to yield pure fine powders of the respective oxides. The microstructures of the oxides were studied by scanning electron microscope photographs.

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“…In general, RE carboxylates are rather simple to synthesize; these compounds are commonly obtained via protolytic or ligand exchange reactions [49][50][51][52][53]. On the other hand, RE coordination compounds are known to exhibit structural flexibility; consequently, both the composition and structure of the synthesis product are highly sensitive to the preparation conditions.…”

Section: Synthesis Of Re Lactatesmentioning

confidence: 99%

Diverse Coordination Chemistry of the Whole Series Rare-Earth L-Lactates: Synthetic Features, Crystal Structure, and Application in Chemical Solution Deposition of Ln2O3 Thin Films

Gashigullin,

Kendin,

Martynova

et al. 2023

Molecules

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Rare-earth (RE, Ln) carboxylates are widely studied as precursors of RE oxide-based nanomaterials; however, no systematic studies of RE L-lactates (HLact = 2-hydroxypropanoic acid) have been reported to date. In the present work, a profound structural investigation of RE L-lactates is carried out. A family of RE lactate complexes of the general formula LnLact3∙nH2O (Ln = La, Ce–Nd, Sm–Lu, Y; n = 2–3) are synthesized and characterized by CHN, TGA, and FTIR as well as by powder and single-crystal XRD methods.The existence of four novel structural types (1-Ln–4-Ln) is revealed. Compounds of the 1-Ln type (Ln = La, Ce, Pr) exhibit a chain polymeric structure, whereas 2-Ln–4-Ln compounds are molecular crystals consisting of dimeric (2-Ln; Ln = La, Ce–Nd) or monomeric (3-Ln–Ln = Sm–Lu, Y; 4-Ln–Ln = Sm–Gd, Y) species. The crystal structures of 1-Ln–4-Ln compounds are discussed in terms of their coordination geometry and supramolecular arrangement. Solutions of yttrium and lanthanum lactates with diethylenetriamine are applied for the chemical deposition of Y2O3 and La2O3 thin films.

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Rare Earth Complexes with Carboxylic Acids, Polyaminopolycarboxylic Acids, and Amino Acids

Cited by 13 publications

References 116 publications

Polytypism and Packing-Dependent Colossal Positive and Negative Thermal Expansion in a 2D Layered Cerium-Based Coordination Polymer

Polytypism and Packing-Dependent Colossal Positive and Negative Thermal Expansion in a 2D Layered Cerium-Based Coordination Polymer

Synthesis, Structure, Antioxidant, and Antiviral Studies on N₂H₅[Ln(edta)(H₂O)₃].5H₂O (Ln = Pr, Nd, and Sm)

Diverse Coordination Chemistry of the Whole Series Rare-Earth L-Lactates: Synthetic Features, Crystal Structure, and Application in Chemical Solution Deposition of Ln2O3 Thin Films

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Rare Earth Complexes with Carboxylic Acids, Polyaminopolycarboxylic Acids, and Amino Acids

Cited by 13 publications

References 116 publications

Polytypism and Packing-Dependent Colossal Positive and Negative Thermal Expansion in a 2D Layered Cerium-Based Coordination Polymer

Polytypism and Packing-Dependent Colossal Positive and Negative Thermal Expansion in a 2D Layered Cerium-Based Coordination Polymer

Synthesis, Structure, Antioxidant, and Antiviral Studies on N2H5[Ln(edta)(H2O)3].5H2O (Ln = Pr, Nd, and Sm)

Diverse Coordination Chemistry of the Whole Series Rare-Earth L-Lactates: Synthetic Features, Crystal Structure, and Application in Chemical Solution Deposition of Ln2O3 Thin Films

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Synthesis, Structure, Antioxidant, and Antiviral Studies on N₂H₅[Ln(edta)(H₂O)₃].5H₂O (Ln = Pr, Nd, and Sm)