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Tetracarbonatodiruthenium Fragments and Lanthanide(III) Ions as Building Blocks to Construct 2D Coordination Polymers.

ABSTRACT: Two-dimensional coordination polymers of [Pr(DMSO)?(OH?)?][Ru?(CO?)?(DMSO)(OH?)]·5H?O (Pr?) and [Ln(OH?)?][Ru?(CO?)?(DMSO)]·xH?O (Ln = Sm (Sm?), Gd (Gd?)) formulae have been obtained by reaction of the corresponding Ln(NO?)?·6H?O dissolved in dimethyl sulphoxide (DMSO) and K?[Ru?(CO?)?]·4H?O dissolved in water. Some DMSO molecules are coordinated to the metal atoms reducing the possibilities of connection between the [Ru?(CO?)?]^3- and Ln³⁺ building blocks giving rise to the formation of two-dimensional networks. The size of the Ln³⁺ ion and the synthetic method seem to have an important influence in the type of two-dimensional structure obtained. Slow diffusion of the reagents gives rise to Pr? that forms a 2D net that is built by Ln³⁺ ions as triconnected nodes and two types of Ru?⁵⁺ units as bi- and tetraconnected nodes with (2-c)(3-c)?(4-c) stoichiometry (? structure). An analogous synthetic procedure gives Sm? and Gd? that display a grid-like structure, (2-c)?(4-c)?, formed by biconnected Ln³⁺ ions and two types of tetraconnected Ru?⁵⁺ fragments (? structure). The magnetic properties of these compounds are basically explained as the sum of the individual contributions of diruthenium and lanthanide species, although canted ferrimagnetism or weak ferromagnetism are observed at low temperature.

SUBMITTER: Gutierrez-Martin D

PROVIDER: S-EPMC6473724 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature

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Tetracarbonatodiruthenium Fragments and Lanthanide(III) Ions as Building Blocks to Construct 2D Coordination Polymers.

Gutiérrez-Martín Daniel D Cortijo Miguel M Martín-Humanes Álvaro Á González-Prieto Rodrigo R Delgado-Martínez Patricia P Herrero Santiago S Priego José L JL Jiménez-Aparicio Reyes R

Polymers 20190305 3

Two-dimensional coordination polymers of [Pr(DMSO)₂(OH₂)₃][Ru₂(CO₃)₄(DMSO)(OH₂)]·5H₂O (Prα) and [Ln(OH₂)₅][Ru₂(CO₃)₄(DMSO)]·xH₂O (Ln = Sm (Smβ), Gd (Gdβ)) formulae have been obtained by reaction of the corresponding Ln(NO₃)₃·6H₂O dissolved in dimethyl sulphoxide (DMSO) and K₃[Ru₂(CO₃)₄]·4H₂O dissolved in water. Some DMSO molecules are coordinated to the metal atoms reducing the possibilities of connection between the [Ru₂(CO₃)₄]3- and Ln3+ buildi ...[more]

PMID: 30960410

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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

Tetracarbonatodiruthenium Fragments and Lanthanide(III) Ions as Building Blocks to Construct 2D Coordination Polymers.

Publications

Tetracarbonatodiruthenium Fragments and Lanthanide(III) Ions as Building Blocks to Construct 2D Coordination Polymers.

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