Lanthanide Oxalatophosphonates Research Articles

Lanthanide oxalatophosphonates with two types of layered structures: syntheses, structures, luminescence and magnetic properties

Five novel lanthanide(iii) oxalatophosphonates with two types of 2D layered structures have been hydrothermally obtained and structurally characterized. The luminescence and magnetic properties of the title compounds have been studied.

A proton-conductive lanthanide oxalatophosphonate framework featuring unique chemical stability: stabilities of bulk phase and surface structure

We select a chemically stable lanthanide oxalatophosphonate framework with proton conductivity as an example, analyzing and evaluating its chemical stability based on the bulk phase and surface structure.

Lanthanide(iii) oxalatophosphonates: syntheses, crystal structures and luminescence properties

By the introduction of oxalate as the second ligand, five new lanthanide oxalatophosphonate hybrids with a 2D layered structure, namely, [Ln(H2L)(C2O4)(H2O)]·2H2O [Ln = Nd (1), Sm (2), Eu (3), Tb (4), Dy (5), H3L = H2O3PCH2NCH2(CH2CH2OPO2H)], have been hydrothermally synthesized and structurally characterized by X-ray single-crystal diffraction, X-ray powder diffraction, infrared spectroscopy, elemental analysis and thermogravimetric analysis. Compounds 1-5 are isostructural and exhibit a 2D layer formed by the interconnection of a 1D zigzag chain of {Ln(C2O4)}(+) with the phosphonate ligands. The effect of lanthanide contraction induces the decrease of the lattice parameters and crystal size from Nd to Dy. The luminescence properties of compounds 2-5 have been studied.

Novel Lanthanide(III) Oxalatophosphonates with New Topology: Syntheses, Crystal Structures, Reversible Dehydration/Hydration, and Luminescence Properties

Hydrothermal reactions of lanthanide(III) chlorides and H2O3PCH2NCH2(CH2CH2OPO2H) (H3L) with oxalate anion lead to six novel lanthanide oxalatophosphonates with a three-dimensional (3D) framework structure, namely, {[Ln(H2L)(C2O4)(H2O)]·nH2O}∞ [n = 3 (compounds 1–3), 2 (compounds 4–6); Ln = Ce (1), Pr (2), Nd (3), Sm (4), Eu (5), and Tb(6)]. Compounds 1–6 are isostructural and feature a complex 3D network built from 1D chains of lanthanide oxalate and {Ln(H2L)}2+ chains. These lanthanide oxalatophosphonates possess two types of channels with dimensions of 11.6 Å × 4.4 Å and 13.8 Å × 8.9 Å along the a- and b-axis, respectively, and these channels incorporate some crystalline water molecules therein by hydrogen-bonding interactions. They show an unusual noninterpenetrated (3,5)-connected topology. The title compounds were characterized by X-ray single-crystal diffraction and X-ray powder diffraction (XRD) as well as with infrared spectroscopy and elemental and thermogravimetric analysis. Furthermore, the temperature-dependent powder XRD, the variable temperature IR spectroscopy, and the dehydration/hydration properties of compound 2 have also been studied. Luminescent measurements indicate that the Sm (4) and Eu (5) compounds exhibit strong luminescence in yellow light and red light regions, respectively.

Isostructural lanthanide oxalatophosphonates Ln(5pm8hqH3)(C2O4)1.5(H2O)·2H2O [Ln(iii) = Eu, Gd, Tb, Dy] (5pm8hqH3 = 5-phosphonomethyl-8-hydroxyquinoline): structures, magnetic and fluorescent properties

Isostructural lanthanide oxalatophosphonates Ln(5pm8hqH3)(C2O4)1.5(H2O)·2H2O [Ln(III) = Eu(1), Gd(2), Tb(3), Dy(4)] have been obtained through hydrothermal reactions of 5-phosphonomethyl-8-hydroxyquinoline (5pm8hqH3), oxalate, and Ln(NO3)3·6H2O. Four compounds reveal layer structures, in which {LnO8} polyhedra are linked through oxalate units into a netlike {Ln(C2O4)1.5}n layer containing 24-member ring composed of six Ln(III) ions and six oxalate anions. The noncoordinated 8-hydroxyquinoline groups protrude from two sides of the layer. Neighboring layers are further connected to each other through hydrogen bonds and aromatic stacking of the 8-hydroxyquinoline rings, forming a supramolecular 3D structure. In magnetic measurements, compound 2 shows weak antiferromagnetic interactions. The magnetic behaviors of 1, 3 and 4 are ascribed to the depopulation of the Stark levels and weak antiferromagnetic interactions. In the solid-state fluorescent measurements, strong ligand-centered emissions and weak Ln(III)-centered emissions can be observed for 1 and 4, while only ligand-centered emissions for 2 and 3.

Hydrothermal synthesis, crystal structures, and luminescent properties of a series of new lanthanide oxalatophosphonates with a layer architecture

Eleven new lanthanide oxalatophosphonate hybrids with a 2D layered structures, namely, [Ln(H(3)L)(C(2)O(4))]·2H(2)O (Ln = La-Dy, Er and Y, H(4)L = C(6)H(5)CH(2)N(CH(2)PO(3)H(2))(2)), have been synthesized under hydrothermal conditions and structurally characterized by X-ray single-crystal diffraction, X-ray powder diffraction, infrared spectroscopy, elemental analysis and thermogravimetric analysis. Compounds 1-11 are isomorphous and they exhibit a 2D framework structure. Two {LnO(8)} polyhedra and four {CPO(3)} tetrahedra are interconnected into a unit via corner-sharing, and the so-built units are bridged by the oxalate anions into a layer. The result of connections in this manner is the formation of a 24-atom window. The thermal stabilities and guest desorption-sorption properties of compounds 1-11 have been investigated. The luminescent properties of compounds 5, 6, 8 and 9 have also been studied.

Two isomorphous 3-D lanthanide oxalatophosphonate frameworks based on glyphosate: syntheses, crystal structures, and luminescence properties

Two new 3-D isomorphous lanthanide(III) compounds [Eu2(H2L)2(C2O4)2]·2.51H2O (1) and [Tb2(H2L)2(C2O4)2]·2.46H2O (2, H3L = glyphosate), based on glyphosate and oxalate have been successfully synthesized under hydrothermal conditions, and structurally characterized. In the two compounds, tetra-connected glyphosate ligands are coordinated to Ln3+, resulting in the formation of 1-D {Ln2(H2L)2}n double chains along the c direction. Each of the chains is connected to its four neighbors via the O atoms of phosphates of H2L− ligands, resulting in a 3-D (4, 6)-connected framework with 43·58·63·7 topology, which possesses 1-D channels with oxalates and lattice water molecules as troglodytes. The oxalates are stabilized via chelating Ln3+ in the form of 1-D Ln-C2O42− zigzag chains along the c direction. To the best of our knowledge, compounds 1 and 2 represent the first single-crystal structures of lanthanide(III)-glyphosate compounds incorporating second ligands. The luminescent properties of compounds 1 and 2 have been investigated at room temperature. The energy gaps between the triplet excited state of oxalic acid and the lowest excited resonance levels of Eu3+ (5D0) and Tb3+ (5D4) are 7270 cm−1 and 4070 cm−1, respectively, indicating that oxalate is more suitable for the sensitization of Tb3+ luminescence than Eu3+ luminescence.

Lanthanide oxalatophosphonates with two- and three-dimensional structures

Reactions of lanthanide nitrate, oxalate sodium and 2-pyridylmethylphosphonic acid (2-pmpH 2) under hydrothermal conditions result in five new lanthanide oxalatophosphonates with two types of structures. Compounds [ Ln 4(ox) 5(2-pmpH) 2(H 2O) 7]·5H 2O [ Ln 3+=Gd ( 1), Tb ( 2), Dy ( 3); ox 2−=C 2O 4 2−] exhibit a double layer structure, made up of net-like { Ln 4(ox) 5} n layers containing Ln 10(ox) 10 rings which are connected by 2-pmpH ‐. While compounds [ Ln 4(ox) 5(2-pmpH) 2(H 2O) 6]·6H 2O [ Ln 3+=Ho ( 4), Yb ( 5)] display a three-dimensional framework structure in which the { Ln 4(ox) 5} n layers are cross-linked by 2-pmpH. The solid state luminescent and magnetic properties are investigated.

Hydrothermal Synthesis, Crystal Structure, and Characterizations of a New Lanthanide Oxalatophosphonate with a 3D Framework Structure

AbstractA new lanthanide oxalatophosphonate with a 3D framework, [Nd2(HL)(C2O4)2(H2O)3]·H2O (1) (H3L = HOOCC5H9NCH2PO3H2) was synthesized by hydrothermal reaction at 140 °C by using carboxyphosphonic acid as phosphonate ligand and oxalate as additional metal linker. It was structurally characterized by single‐crystal as well as powder X‐ray diffraction methods, infrared spectroscopy, elemental analysis, and thermogravimetric analysis. In compound 1, the interconnection of the neodymium(III) ions by chelating and bridging oxalate anions leads to a neodymium oxalate layer, these layers are further bridged by carboxyphosphonate ligands to form a 3D framework structure. It is interesting that the result of these connections is the formation of 20‐ and 16‐atom rings that are parallel to one another and run in the b axis direction.

Syntheses, Crystal Structures, and Luminescence Properties of a Series of Novel Lanthanide Oxalatophosphonates with Two Types of 3D Framework Structures

By introduction of oxalate as the second ligand, 12 novel lanthanide oxalatophosphonates with two types of three-dimensional (3D) framework structures, namely, [Ln2(H4L)(C2O4)3(H2O)]·3H2O (Ln = La ...

Seven Novel Lanthanide Oxalatophosphonates with Two Types of 3D Framework Structures Based on N-Morpholinomethylphosphonic Acid: Syntheses, Crystal Structures, and Luminescence Properties

By using the N-morpholinomethylphosphonic acid as the phosphonate ligand and oxalate as the second metal linker, seven novel lanthanide(III) oxalatophosphonates with two types of 3D framework structures, namely, [Ln3(HL)(C2O4)4(H2O)4]·2H2O (Ln = Pr (1), Nd (2), Sm (3), H2L = O(CH2CH2)2NCH2PO3H2) and [Ln2(H2L)(C2O4)3(H2O)3]·H2O (Ln = Eu (4), Gd (5), Tb (6), Dy (7)), have been synthesized under hydrothermal conditions. Compounds 1−3 are isostructural and feature a complex 3D framework structure formed by the interconnection of 3D network of {Ln3(C2O4)4}+ with 1D chains of {Ln3(HL)}8+. Compounds 4−7 are isostructural and possess a 3D framework structure different from that in compounds 1−3. The interconnection of Ln(III) ions by chelating oxalate ligands lead to a lanthanide oxalate layer down the c-axis. These layers are linked by H2L ligands to form a 3D framework type with channel system down the a-axis. Luminescence properties of compounds 3, 4, 6 and 7 have also been studied.

Synthesis, crystal structures and luminescence properties of lanthanide oxalatophosphonates with a three-dimensional framework structure

Six new three-dimensional (3D) lanthanide oxalatophosphonates, [Ln(HL)(C2O4)0.5(H2O)2]·H2O (Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6); H3L = H2O3PCH(OH)CO2H), have been synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction as well as by infrared spectroscopy, elemental analysis and thermogravimetric analysis. Compounds 1–6 are isomorphous and they exhibit a complex three-dimensional (3D) open-framework structure with a one-dimensional channel system along the c-axis. The interconnection of the lanthanide(III) ions by phosphonate ligands results in a lanthanide phosphonate layer, and these layers are further bridged by oxalate anions to form a 3D open-framework. Compound 6 shows strong red luminescence in the solid state at room temperature.

Synthesis, crystal structure and characterizations of a novel lanthanide oxalatophosphonate with a 3D open-framework structure [Gd 2{HO 3PCH 2NHCH 2(CH 2CH 2OPO 2)}(C 2O 4) 2.5(H 2O) 2] · 5H 2O

A novel lanthanide oxalatophosphonate, [Gd 2{HO 3PCH 2NHCH 2(CH 2CH 2OPO 2)}(C 2O 4) 2.5(H 2O) 2] · 5H 2O 1 has been synthesized by hydrothermal reaction at 140 °C and structurally characterized by single-crystal X-ray diffraction as well as with infrared spectroscopy, elemental analysis and thermogravimetric analysis. The interconnection of gadolinium(Ш) ions by bridging H 2L – anions leads to a 3D open-framework structure with channels along the a-axis. The channel is formed by 44-membered rings composed of six gadolinium(Ш) ions and six H 2L – anions. The chelating and bridging oxalates are found on the surface of the channels extending along the a direction.