One-Pot Hydrothermal Synthesis of TbIII13(GeO4)6O7(OH) and K2TbIVGe2O7: Preparation of a Stable Terbium(4+) Complex

Fulle, Kyle; Sanjeewa, Liurukara D.; McMillen, Colin D.; Wen, Yimei; Rajamanthrilage, Apeksha C.; Anker, Jeffrey N.; Chumanov, George; Kolis, Joseph W.

doi:10.1021/acs.inorgchem.7b00821

Cited by 16 publications

(2 citation statements)

References 39 publications

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“…Until recently, when the first oxoanionic salts of Tb 4+ and metal organic complexes of both ions were published, Pr 4+ and Tb 4+ were known to exist almost exclusively in solid oxides and fluorides. − Some oxoanionic salts of Pr 4+ were reported in the 1960s in a series of communications by Pajakoff in the form of various sulfates along with nitrates, oxalates, and even carbonates. − Despite these early reports that contain no structural data, the published compounds were never reproduced until today, and the proposed compositions were thus never confirmed by X-ray diffraction (XRD) experiments or other techniques. Reports on analogous compounds of Tb 4+ have also not been published, despite the similar oxidation potential of both tetravalent cations (Pr 3+ /Pr 4+ : E 0 = 3.2 V; Tb 3+ /Tb 4+ : E 0 = 3.1 V). , Hence, no oxoanionic salt containing Pr 4+ has been structurally characterized thus far.…”

Section: Introductionmentioning

confidence: 99%

Stabilization of Pr⁴⁺ in Silicates─High-Pressure Synthesis of PrSi₃O₈ and Pr₂Si₇O₁₈

Flosbach,

Bykov,

Bykova

et al. 2024

Inorg. Chem.

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The reaction between PrO 2 and SiO 2 was investigated at various pressure points up to 29 GPa in a diamond anvil cell using laser heating and in situ single-crystal structure analysis. The pressure points at 5 and 10 GPa produced Pr 2 III (Si 2 O 7 ), whereas Pr 4 III Si 3 O 12 and Pr 2 IV (O 2 )O 3 were obtained at 15 GPa. Pr 4 III Si 3 O 12 can be interpreted as a high-pressure modification of the still unknown orthosilicate Pr 4 III (SiO 4 ) 3 . Pr IV Si 3 O 8 and Pr 2 IV Si 7 O 18 that contain praseodymium in its rare + IV oxidation state were identified at 29 GPa. After the pressure was released from the reaction chamber, the Pr(IV) silicates could be recovered, indicating that they are metastable at ambient pressure. Density functional theory calculations of the electronic structure corroborate the oxidation state of praseodymium in both Pr IV Si 3 O 8 and Pr 2 IV Si 7 O 18 . Both silicates are the first structurally characterized representatives of Pr 4+ -containing salts with oxoanions. All three silicates contain condensed networks of [SiO 6 ] octahedra which is unprecedented in the rich chemistry of lanthanoid silicates.

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Section: Introductionmentioning

confidence: 99%

Stabilization of Pr⁴⁺ in Silicates─High-Pressure Synthesis of PrSi₃O₈ and Pr₂Si₇O₁₈

Flosbach,

Bykov,

Bykova

et al. 2024

Inorg. Chem.

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“…ThO2:Tb 4+ ), 29,30 bulk binary terbium oxides and fluorides (TbO2 and TbF4), 31,32 and other extended solids. [33][34][35][36][37] Electron paramagnetic resonance (EPR) and X-ray absorption spectroscopy (XAS) studies of these solid-state terbium complexes and related tetravalent lanthanide and actinide complexes indicate that the increased covalent bonding present in (E) X-ray crystal structures of 3 and 4 with thermal ellipsoids at 50% probability. Black, blue, yellow, red, and aqua represent carbon, nitrogen, phosphorous, oxygen and terbium, respectively.…”

Section: Introductionmentioning

confidence: 99%

Design, Isolation, and Spectroscopic Analysis of a Tetravalent Terbium Complex

Rice¹,

Popov²,

Russo³

et al. 2019

Preprint

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Synthetic strategies to yield molecular complexes of high-valent lanthanides, other than the ubiquitous Ce4+ ion, are exceptionally rare, and thorough, detailed characterization in these systems is limited by complex lifetime and reaction and isolation conditions. The synthesis of high-symmetry complexes in high purity with significant lifetimes in solution and solid-state are essential for determining the role of ligand-field splitting, multiconfigurational behavior, and covalency in governing the reactivity and physical properties of these potentially technologically transformative tetravalent ions. We report the synthesis and physical characterization of an S4 symmetric, four-coordinate tetravalent terbium complex, [Tb(NP(1,2-bis-tBu-diamidoethane)(NEt2))4] (where Et is ethyl and tBu is tert-butyl). The ligand field in this complex is weak and the metal-ligand bonds sufficiently covalent so that the tetravalent terbium ion is stable and accessible via a mild oxidant from the anionic, trivalent, terbium precursor, [(Et2O)K][Tb(NP(1,2-bis-tBu-diamidoethane)(NEt2))4]. The significant stability of the tetravalent complex enables its thorough characterization. The step-wise development of the supporting ligand points to key ligand control elements for further extending the known tetravalent lanthanide ions in molecular complexes. Magnetic susceptibility, electron paramagnetic resonance (EPR) spectroscopy, X-ray absorption near-edge spectroscopy (XAS), and density functional theory studies indicate a 4f7 ground state for [Tb(NP(1,2-bis-tBu-diamidoethane)(NEt2))4] with considerable zero-field splitting: demonstrating that magnetic, tetravalent lanthanide ions engage in covalent metal-ligand bonds. This result has significant implications for the use of tetravalent lanthanide ions in magnetic applications since the observed zero-field splitting is intermediate between that observed for the trivalent lanthanides and for the transition metals. The similarity of the multiconfigurational behavior in the ground state of [Tb(NP(1,2-bis-tBu-diamidoethane)(NEt2))4] (measured by Tb L3-edge XAS) to that observed in TbO2 implicates ligand control of multiconfigurational behavior as a key component of the stability of the complex.

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Utilizing an In Situ Reduction in the Synthesis of BaMoOF5

2019

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One-Pot Hydrothermal Synthesis of Tb^III₁₃(GeO₄)₆O₇(OH) and K₂Tb^IVGe₂O₇: Preparation of a Stable Terbium(4+) Complex

Cited by 16 publications

References 39 publications

Stabilization of Pr⁴⁺ in Silicates─High-Pressure Synthesis of PrSi₃O₈ and Pr₂Si₇O₁₈

Stabilization of Pr⁴⁺ in Silicates─High-Pressure Synthesis of PrSi₃O₈ and Pr₂Si₇O₁₈

Design, Isolation, and Spectroscopic Analysis of a Tetravalent Terbium Complex

Utilizing an In Situ Reduction in the Synthesis of BaMoOF5

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One-Pot Hydrothermal Synthesis of TbIII13(GeO4)6O7(OH) and K2TbIVGe2O7: Preparation of a Stable Terbium(4+) Complex

Cited by 16 publications

References 39 publications

Stabilization of Pr4+ in Silicates─High-Pressure Synthesis of PrSi3O8 and Pr2Si7O18

Stabilization of Pr4+ in Silicates─High-Pressure Synthesis of PrSi3O8 and Pr2Si7O18

Design, Isolation, and Spectroscopic Analysis of a Tetravalent Terbium Complex

Utilizing an In Situ Reduction in the Synthesis of BaMoOF5

Contact Info

Product

Resources

About

One-Pot Hydrothermal Synthesis of Tb^III₁₃(GeO₄)₆O₇(OH) and K₂Tb^IVGe₂O₇: Preparation of a Stable Terbium(4+) Complex

Stabilization of Pr⁴⁺ in Silicates─High-Pressure Synthesis of PrSi₃O₈ and Pr₂Si₇O₁₈

Stabilization of Pr⁴⁺ in Silicates─High-Pressure Synthesis of PrSi₃O₈ and Pr₂Si₇O₁₈