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Synthesis, structure, and luminescent properties of a family of lanthanide-functionalized peroxoniobiophosphates.

ABSTRACT: Eight new lanthanide derivatives containing 6-peroxoniobio-4-phosphate building block, [Ln^III(H₂O)₆]₂[H₄(NbO₂)₆P₄O₂₄]·nH₂O [Ln?=?Eu (1), Gd (2), Tb (3), Dy (4), Ho (5), Er (6), Tm (7), Yb (8), 1-5, 7, 8 n?=?12; 6 n?=?9], have been successfully obtained using an in-situ strategy and fully characterized in the solid state by single-crystal X-ray diffraction, IR spectra, TG-MS, PXRD. Structural analyses indicate that these isostructural polyanions 1-8 consist of one [P₄(NbO₂)₆O₂₄]^10- (P ₄ (NbO ₂ ) ₆ ) clusters and two pendant Ln³⁺ cations. In these compounds, P ₄ (NbO ₂ ) ₆ clusters are connected by lanthanide cations to form extended two-dimensional architectures. The approach takes advantage of the ability of in-situ formed P ₄ (NbO ₂ ) ₆ cluster to build frameworks by using it as ligands to lanthanide ions. The photoluminescence (PL) and lifetime decay behaviors of 1, 3 and 4 in solid state have been performed at room temperature. The PL emission of 1, 3 and 4 is mainly derived from the characteristic ⁵D₀?⁷F_J (J?=?1, 2, 3, 4), ⁵D₄?⁷F_J (J?=?6, 5, 4, 3) and ⁴F_9/2?⁶H _J (J?=?15/2, 13/2, 11/2) transitions of the Eu^III, Tb^III and Dy^III cations, respectively.

SUBMITTER: Wang H

PROVIDER: S-EPMC5587641 | biostudies-literature | 2017 Sep

REPOSITORIES: biostudies-literature

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Synthesis, structure, and luminescent properties of a family of lanthanide-functionalized peroxoniobiophosphates.

Wang Haiying H Li Jing J Sun Junjun J Wang Yaya Y Liang Zhijie Z Ma Pengtao P Zhang Dongdi D Wang Jingping J Niu Jingyang J

Scientific reports 20170906 1

Eight new lanthanide derivatives containing 6-peroxoniobio-4-phosphate building block, [LnIII(H2O)6]2[H4(NbO2)6P4O24]·nH2O [Ln = Eu (1), Gd (2), Tb (3), Dy (4), Ho (5), Er (6), Tm (7), Yb (8), 1-5, 7, 8 n = 12; 6 n = 9], have been successfully obtained using an in-situ strategy and fully characterized in the solid state by single-crystal X-ray diffraction, IR spectra, TG-MS, PXRD. Struct ...[more]

PMID: 28878281

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Project description:Five new Lanthanide(III) complexes of malonic acid (HOOC-CH2-COOH); {[Gd(C3H2O4)(H2O)4]·NO3} n (1), {[Tb(C3H2O4)(H2O)4]·NO3} n (2), {[Ho(C3H2O4)(H2O)4]·NO3} n (3), [Er(C3H2O4)(C3H3O4)(H2O)2] n (4), and {[Eu2(C3H2O4)2(C3H3O4)2(H2O)6]·4H2O} n (5) were synthesized and characterized by elemental, infrared spectral, and thermal analyses. The structures of compounds 1-5 were determined by single crystal X-ray diffraction technique. The X-ray analysis reveals that compounds 1, 2, and 3 are isostructural and crystallized in the orthorhombic space group Pmn21. The lanthanide(III) ions are coordinated by four carboxylate and four water oxygen atoms adopting a distorted square antiprism geometry. The LnO8 square antiprisms are linked into infinite layers by malonate (C3H2 O42- ) dianions sandwiching sheets of nitrate counter ions. Compound 4 contains ErO8 square antiprisms linked into a two-dimensional network by hydrogen malonate (C3H3 O4- ) anions and malonate dianions. The europium complex, 5 is dinuclear having the two europium(III) ions (Eu1 and Eu2) bridged by carboxylate groups of hydrogen malonate ligands. The europium ions in 5 are nine-coordinate and exhibit a distorted monocapped square antiprism geometry. All the structures are consolidated by O-H??O hydrogen bonds. The photoluminescence spectra of 1-5 exhibit characteristic emissions in the visible region. The IR spectra and thermal data are consistent with the structural results. The room-temperature effective magnetic moments for 1-4 are in good agreement with those expected for the free ions, while the data for 5 indicates that low-lying excited states contribute to the observed moment. The compound 1 was further subjected to quantum computational calculations to explore its optoelectronic properties including; density of states (DOS), dielectric function, refractive index, extinction coefficient, and absorption spectrum, to highlight the possible applications of such materials in the optoelectronics.

Dataset Information

Synthesis, structure, and luminescent properties of a family of lanthanide-functionalized peroxoniobiophosphates.

Publications

Synthesis, structure, and luminescent properties of a family of lanthanide-functionalized peroxoniobiophosphates.

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