Synthesis, crystal structure and luminescence properties of two novel lanthanide coordination polymers containing double chain

Two novel lanthanide(III) two-dimensional (2D) coordination polymers [Ln₂(PDC)₂(OH)₂(H₂O)₂] · H₂O (Ln = Eu (1) and Tb (2), H₂PDC = pyridine-3,4-dicarboxylic acid) have been prepared under hydrothermal conditions and characterized by elemental analysis, IR, TGA and single-crystal X-ray diffraction. Compounds 1 and 2 crystallize in the triclinic system, space group , they are isostructural and exhibit the same two-dimensional topological network constructed by PDC-connected Ln-O-Ln double chains. Photoluminescence properties of the compounds 1 and 2 have been investigated in the solid state at room temperature.     

In situ hydrothermal syntheses, crystal structures and luminescent properties of two novel zinc(II) coordination polymers based on tetrapyridyl ligand

Two novel Zn(II) coordination polymers, [Zn(2-pytpy)(fum)]_n·nH₂O (1) and [Zn₆(4-pytpy)₃(mal)₄]_n·5n(H₂O) (2), (2-pytpy = 4′-(4-pyridyl)-2,2′:6′,2″-terpyridine, 4-pytpy = 4′-(4-pyridyl)-4,2′:6′,4″-terpyridine, H₂fum = fumaric acid and H₂mal = malic acid) have been hydrothermally synthesized and structurally characterized. Notably, in situ ligand reactions occur in the formation of complexes 1 and 2, in which maleic acid is converted into fumaric acid and malic acid, respectively. Complex 1 is a 1D infinite chain structure, which is extended into a supramolecular layer by intermolecular π…π stacking interactions. Complex 2 is a 3D network structure, in which the bidentate-bridging 4-pytpy ligands link the layers based on the tetranuclear Zn(II) subunits to form the (4,10)-connected network. The luminescent properties of 1 and 2 have been investigated with emission spectra and UV-Vis diffuse reflectance spectra in the solid state. Additionally, these two complexes possess great thermal stabilities.     

Hydrothermal syntheses, structures and properties of five rare earth coordination polymers with (1,3,4-thiadiazole-2,5-diyldithio)diacetic acid

Hydrothermal reactions of rare earth ions(III) with a flexible building unit (1,3,4-thiadiazole-2,5-diyldithio)diacetic acid (H₂tzda) lead to five novel coordination polymers with 1D chain and 3D network structures, namely, {[Y₂(tzda)₃(H₂O)₁₀] · 5H₂O}_n (1) and [Ln₂(tzda)₃(H₂O)₅]_n [Ln = Er (2), Pr (3), Nd (4), Eu (5)]. Compound 1 has one-dimensional ribbon-like chain structure constructed by [Y₂(tzda)₃] units through the syn-anti bidentate bridging mode of carboxylate groups. Compounds 2-5 possess compact three-dimensional network structures which are made up of [Ln₂(tzda)₃] (Ln = Er, Pr, Nd and Eu) units bridged by carboxylate groups. In these compounds, the flexible tzda²⁻ ligand is versatile and displays six different coordination fashions to meet the requirement of the coordination preference of the metal center. Furthermore, the magnetic behaviors for 2-5 in the temperature range of 5.0-300 K and photoluminescent property of 5 are significantly investigated in this paper.     

Syntheses, crystal structures and magnetic properties of 1D and 2D cobaltous coordination polymers with mixed ligands

Two new Co(II) coordination polymers with mixed ligands, {[Co(BTA)_0.5(DBI)₂]·DBI·H₂O}_n (1) and [Co(PDA)(DBI)(H₂O)]_n (2) (H₄BTA = benzene-1,2,4,5-tetracarboxylic acid; H₂PDA = 2,2′-(1,2-phenylene)diacetic acid; DBI = 5,6-dimethyl-1H-benzoimidazole) have been synthesized under hydrothermal conditions, respectively. Both of them are characterized by elemental analyses, powder X-ray diffraction, thermogravimetric analysis, single-crystal X-ray diffraction, and magnetic susceptibilities. In 1, the Co(II) ions are four-coordinated and lie in distorted tetrahedron coordination environment. 1D ladder-like chain structure is formed by the bridging BTA⁴⁻ ligand. In 2, the Co(II) ions are in slightly distorted octahedral coordination geometry, and linked by PDA²⁻ ligand exhibiting a 2D layer structure. Temperature-dependent magnetic susceptibility measurements of 1 and 2 revealed that there are antiferromagnetic interactions between Co(II) ions.     

Hydrothermal synthesis and crystal structures of two lanthanide coordination polymers with novel tetradentate-coordinated perchlorates

Two new 3D lanthanide coordination polymers {[Ln(C₂O₄)(ClO₄)(H₂O)] · Cl}_n [Ln = Pr (1) and Nd (2)] have been synthesized by hydrothermal reactions and characterized by elemental analysis, X-ray single-crystal analyses, IR and Raman spectroscopy. X-ray crystal structure analyses reveal that compounds 1 and 2 are isostructural and crystallized in the space group P2₁/c. A 1D zigzag chains formed by oxalate ligands in μ₂-mode to bridge Ln(III) atoms present in the two complexes and the adjacent zigzag chains were further connected by μ₃-η¹:η¹:η¹:η¹ fashion of into a 3D framework with ordered 1D channels, in which uncoordinated Cl⁻ anions are located as counterions. In addition, the IR and Raman spectrum further confirm the presence of tetradentate-coordinated perchlorates.     

Synthesis, structures and thermal properties of three new two-dimensional coordination networks assembled by lanthanide salts and carboxylate ligand

Three new rare-earth coordination polymers, [La₂(PDC)₂(NO₃)₂(H₂O)₃] (1) and [Dy(PDC)(ox)_0.5(H₂O)₂] · H₂O (2), and [Sm(PDC)(ox)_0.5(H₂O)₂] · H₂O (3) (H₂PDC = pyridine-3,4-dicarboxylic acid, ox = oxalic acid), have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, TGA, and single-crystal X-ray diffraction. Of the three compounds, La-O-La and Dy(Sm)-O-C-O-Dy(Sm) chains are cross-linked by PDC ligands into interesting two-dimensional framework structures. They represent, to the best of our knowledge, the first examples of rare-earth complexes in the {M/PDC} (M = metal) system.     

Hydrothermal syntheses, crystal structures and characterizations of three new copper coordination polymers

Three new copper complexes, [Cu^IICu^I(ip)(ipH)(4,4′-bipy)_3/2]_n (1), [Cu(ip)(4,4′-bipy)]_n · 3nH₂O (2), and [Cu(ipH)₂(4,4′-bipy)]_n (3), have been hydrothermally synthesized by the reaction of Cu(NO₃)₂ · 3H₂O with isophthalic acid (ipH₂) and 4,4′-bipyridine (4,4′-bipy) under different reaction conditions. Complex 1, a mixed-valence copper(I,II) complex, exhibits a 2-D interpenetrating grid framework, in which five-coordinated Cu^II and three-coordinated Cu^I environments are established. The oxidation states of center Cu atoms have been confirmed by X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance spectra (EPR). Complex 2 features a 2-D box-like bilayer architecture, in which Cu^II atoms are linked by ip ligands to form a 1-D double-chain and the resulting chains are further strutted by the 4,4′-bipy ligands. In complex 3, two bridging 4,4′-bipy ligands and two terminal ipH ligands confine the Cu^II center in a square plane coordination geometry. The whole molecule of 3 was arranged into a 1-D linear chain structure. Additionally, the thermogravimetric analyses (TGA) for complexes 1-3 are also discussed in this paper.     

Synthesis, crystal structures and magnetic behavior of two 3D coordination polymers using N-(4/3-carboxyphenyl)iminodiacetic acids as bridging ligands

Research on structure and magnetic properties of polynuclear metal complexes to understand the structural and chemical factors governing the electronic exchange coupling mediated by multi-atom bridging ligands is of growing interest. Hydrothermal treatment of Ni(NO₃)₂·6H₂O with N-(4-carboxyphenyl)iminodiacetic acid [N-4(H₃CPIDA)] at 150 °C yielded a 3D coordination polymer of general formula [Ni₃{N-4(CPIDA)}₂(H₂O)₃]·6H₂O (1). An analogous network of general formula [Co₃{N-3(CPIDA)}₂(H₂O)₃]·3H₂O (2) was synthesized using N-(3-carboxyphenyl)iminodiacetic acid [N-3(H₃CPIDA)] in combination with Co(NO₃)₂·6H₂O under identical reaction condition. Both the complexes contain trinuclear secondary building unit, and crystallized in monoclinic system with space groups C2/c (1) and P2₁/c (2), respectively. Variable temperature magnetic characterization of these complexes in the temperature range of 2-300 K indicated the presence of overall ferromagnetic and antiferromagnetic behavior for 1 and 2, respectively. Density functional theory calculations (B3LYP functional) were performed for further insight on the trinuclear units to provide a qualitative theoretical interpretation on the overall magnetic behavior of the complexes 1 and 2.     

Aromatic N-oxide bridged copper(II) coordination polymers: Synthesis, characterization and magnetic properties

The complexes [Cu₂(o-NO₂-C₆H₄COO)₄(PNO)₂] (1), [Cu₂(C₆H₅COO)₄(2,2′-BPNO)]_n (2), [Cu₂(C₆H₅COO)₄(4,4′-BPNO)]_n (3), [Cu(p-OH-C₆H₄COO)₂(4,4′-BPNO)₂·H₂O]_n (4), (where PNO = pyridine N-oxide, 2,2′-BPNO = 2,2′-bipyridyl-N,N′-dioxide, 4,4′-BPNO = 4,4′-bipyridyl-N,N′-dioxide) are prepared and characterized and their magnetic properties are studied as a function of temperature. Complex 1 is a discrete dinuclear complex while complexes 2-4 are polymeric of which 2 and 3 have paddle wheel repeating units. Magnetic susceptibility measurements from polycrystalline samples of 1-4 revealed strong antiferromagnetic interactions within the {Cu₂}⁴⁺ paddle wheel units and no discernible interactions between the units. The complex 5, [Cu(NicoNO)₂·2H₂O]_n·4nH₂O, in which the bridging ligand to the adjacent copper(II) ions is nicotinate N-oxide (NicoNO) the transmitted interaction is very weakly antiferromagnetic.     

Two novel three-dimensional coordination polymers based on metal clusters: Hydrothermal syntheses, crystal structures and luminescence

Two novel coordination polymers with interesting supramolecular architecture, [Zn₂(OH)(BTC)(bix)] (1) and [Cd₂(CDC)₂(bix)₂] (2) (H₃BTC = 1,3,5-benzenetricarboxylic acid, H₂CDC = trans-1,4-cyclohexanedicarboxylic acid and bix = 1,2-bis(imidazol-1-ylmethyl)benzene) have been obtained via hydrothermal reaction and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Complex 1 features a 3D network with one of the scarce (3,8)-connected (4³)₂(4⁶.6¹⁸.8⁴) topology based on the rare CdI₂-type layer constructed from secondary building units (SBUs) of zinc clusters. While 2 exhibits a scarcely reported eight-connected 3⁶.4¹⁶.5⁶ net with dinuclear cadmium clusters as secondary building units. The luminescent properties of 1 and 2 along with the bix ligand in the solid state were investigated.     

Crystal structures and third-order NLO properties in DMF solution of Co(II)-bpfp coordination polymers (bpfp=N,N-bis(pyridylformyl)piperazine)

Two novel Co(II) coordination polymers {[Co(H₂O)₂(CH₃OH)₂(4-bpfp)](NO₃)₂}_n1 (4-bpfp=N,N^′-bis(4-pyridylformyl)piperazine) and [Co(NCS)₂(CH₃OH)₂(3-bpfp)]_n2 (3-bpfp=N,N^′-bis(3-pyridylformyl)piperazine) have been synthesized and characterized by single crystal X-ray diffraction. Both the polymers consist of one-dimensional chains constructed by bridging bpfp ligands and Co(II) ions. The existence of O?H-O hydrogen bond in 1 and S?H-O hydrogen bond in 2 play important roles in creating interesting supramolecular structures. Their third-order nonlinear optical (NLO) properties in DMF solution have been studied by Z-scan technique. The results reveal that polymers 1 and 2 exhibit strong NLO absorption effects (α₂=9.00×10⁻¹¹ m W⁻¹ for 1; 1.41 × 10⁻¹⁰ m W⁻¹ for 2) and self-focusing performance (n₂=3.24×10⁻¹⁶ esu for 1; 3.05 × 10⁻¹⁶ esu for 2) in DMF solutions. The corresponding effective NLO susceptibilities χ⁽³⁾ values are 3.08 × 10⁻¹² esu (1) and 4.70 × 10⁻¹² esu (2). All of the values are comparable to those of the reported good NLO materials. Additionally, the TG-DTA results of the two polymers are in agreement with the crystal structures.     

Hydrothermal synthesis, crystal structure and magnetic characterization of two 4f-3d heterometallic coordination polymers

Two new 4f-3d heterometallic coordination polymers [Gd₂Co(L₁)₃(ox)(H₂O)₄]·2.5H₂O (1, L₁ = pyridine-2,5-dicarboxylate anion, ox = oxalate dianion) and [GdNi(L₂)₂(ox)_0.5(H₂O)₃]·3H₂O (2, L₂ = pyridine-2,3-dicarboxylate anion) were successfully synthesized under hydrothermal conditions. In compound 1, one dimensional heterometallic and lanthanide infinite sheets were constructed with sole L₁ spacers and L₁-ox mixed bridges, respectively. While similar one dimensional heterometallic infinite sheet and normal lanthanide infinite zigzag chain were formed based on sole L₂ and L₂-ox mixed bridges, respectively in compound 2. Both of the two compounds exhibited new and interesting three dimensional topologies. In addition, the magnetic properties of the two compounds were analyzed via solid-state dc magnetic susceptibility measurements.     

Equilibrium and structural studies on Co(II), Ni(II), Cu(II) and Zn(II) complexes with N-(2-benzimidazolyl)methyliminodiacetic acid: crystal structures of Ni(II) and Cu(II) complexes

Combined pH-metric, UV-Vis, ¹H NMR and EPR spectral investigations on the complex formation of M(II) ions (M=Co, Ni, Cu and Zn) with N-(2-benzimidazolyl)methyliminodiacetic acid (H₂bzimida, hereafter H₂L) in aqueous solution at a fixed ionic strength, I=10⁻¹ mol dm⁻³, at 25 ± 1 °C indicate the formation of M(L), M(H₋₁L)⁻ and M₂(H₋₁L)⁺ complexes. Proton-ligand and metal-ligand constants and the complex formation equilibria have been elucidated. Solid complexes, [M(L)(H₂O)₂] · nH₂O (n=1 for M = Co and Zn, n=2 for M = Ni) and {Cu (μ-L) · 4H₂O}_n, have been isolated and characterized by elemental analysis, spectral, conductance and magnetic measurements and thermal studies. Structures of [Ni(L)(H₂O)₂] · 2H₂O and {Cu(μ-L) · 4H₂O}_n have been determined by single crystal X-ray diffraction. The nickel(II) complex exists in a distorted octahedral environment in which the metal ion is coordinated by the two carboxylate O atoms, the amino-N atom of the iminodiacetate moiety and the pyridine type N-atom of the benzimidazole moiety. Two aqua O atoms function as fifth and sixth donor atoms. The copper(II) complex is made up of interpenetrating polymeric chains of antiferromagnetically coupled Cu(II) ions linked by carboxylato bridges in syn-anti (apical-equatorial) bonding mode and stabilized via interchain hydrogen bonds and π-π stacking interactions.     

Metal-dependent dimensionality in coordination polymers of a semi-rigid dicarboxylate ligand with additional amide groups: Syntheses, structures and luminescent properties

Three new coordination polymers, [CdL(H₂O)₃·H₂O]_n (1), [MnL(H₂O)₂]_n (2) and [ZnL]_n (3) (L = 2,2′-[1,4-bis(-benzamido)]diacetate) have been hydrothermally synthesized. Complex 1 and complex 2 are 1-D infinite zigzag chain and 2-D rectangular grid networks, respectively, in which are further stabilized by hydrogen bonds, thus affording two 3-D supramolecular frameworks. Complex 3 exhibits a (4, 4)-connected PtS topology. Moreover, an unusual phenomenon has been observed that the dimension of these coordination polymers gradually increases with the decrease of coordination numbers of metal ions. In addition, complex 1 exhibits a strong blue luminescence in the solid state at room temperature and may be potential candidate for luminescent materials.     

Two cadmium-thiocyanate coordination polymers with organic cations: Synthesis, crystal structures and luminescent properties

Two new inorganic-organic hybrid polymers [ClBzQl]₂[Cd(SCN)_3.5Br_0.5]·0.25H₂O (1) and [ClBzMePy][Cd(SCN)₃] (2) (ClBzQl = 1-(4′-Cl-benzyl)quinolinium cation and ClBzMePy = 1-(4′-Cl-benzyl)-2-methylpyridinium cation) have been synthesized and characterized by IR, UV, elemental analysis and X-ray crystallography. Crystal structure analyses show that two polymers belong to the monoclinic space group P2/n (1) and P2₁/c (2) with a = 18.548(2) Å, b = 9.526(1) Å, c = 20.689(2) Å, β = 94.008(1)°, V = 3646.6(5) Å³ for 1, and a = 11.195(2) Å, b = 16.415(3) Å, c = 10.751(2) Å, β = 102.930(3)°, V = 1925.7(7) Å³ for 2. The Cd atom exhibits a distorted octahedral coordination geometry for 1 and 2. For 1, a pair of 1,1-μ-SCN⁻ anions and a pair of 1,3-μ-SCN⁻ anions are alternately bridge adjacent Cd centers to form infinite polymeric chains. For 2, adjacent Cd atoms are linked by three 1,3-μ-SCN⁻ anions to form infinite [Cd(SCN)₃⁻]_∞ polymeric chains. The luminescent properties of the two polymers in the solid state at room temperature were investigated.     

First examples of ternary lanthanide 2,2′-bipyridine-3,3′-dicarboxylate coordination polymers with zigzag chains structures assembled from lanthanide ions, 2,2′-bipyridine-3,3′-dicarboxylate and 1,10-phenanthroline

Four lanthanide coordination polymers, [{Ln₂(bpdc)₃(phen)₂(H₂O)₂} · (H₂O)₆]_n (Ln = Sm (1); Eu (2); Gd (3), Tb (4)), were self-assembled from 2,2′-bipyridine-3,3′-dicarboxylic acid (H₂bpdc),1,10-phenanthroline(phen) and corresponding lanthanide oxides by hydrothermal synthesis. Compounds 1-4 are found to be isomorphous and isostructural. Single-crystal X-ray diffraction studies show that compounds 1-4 are all of one-dimensional zigzag chain structures and extend to two-dimensional networks through π-π interactions and hydrogen bonds. The pyridyl nitrogen atoms of the 2,2′-bipyridyl unit in the bpdc ligand are uncoordinated in an anti-conformation along the central C-C bond of the ligand. Thermogravimetric analysis of 1-4 showed an obvious thermal stability indicating that the coordination habit of the metal ions with bpdc and phen has an effect on the overall framework. Photoluminescence measurement indicates that compound 2 and compound 4 are strong red and green emitters, respectively.     

Preparation, crystal structure and luminescent properties of lanthanide picrate complexes with N-benzyl-2-{2′-[(benzyl-methyl-carbamoyl)-methoxy]-biphenyl-2-yloxy}-N-methyl-acetamide (L)

A new amide-based ligand derived from biphenyl, N-benzyl-2-{2′-[(benzyl-methyl-carbamoyl)-methoxy]-biphenyl-2-yloxy}-N-methyl-aceamide (L) was synthesized. Solid complexes of lanthanide picrates with this new ligand were prepared and characterized by elemental analysis, conductivity measurements, IR and electronic spectroscopies. The molecular structure of [Eu(pic)₃L] shows that the Eu(III) ion is nine-coordinated by four oxygen atoms from the L and five from two bidentate and one unidentate picrates. All the coordinate picrates and their adjacent equivalent picrates form intermolecular π-π stacking. Furthermore, the [Eu(pic)₃L] complex units are linked by the π-π stacking to form a two-dimensional (2-D) netlike supramolecule. Under excitation, the europium complex exhibited characteristic emissions. The lifetime of the ⁵D₀ level of the Eu(III) ion in the complex is 0.22 ms. The quantum yield Φ of the europium complex was found to be 1.01 × 10⁻³ with quinine sulfate as reference. The lowest triplet state energy level of the ligand indicates that the triplet state energy level of the ligand matches better to the resonance level of Eu(III) than Tb(III) ion.     

Syntheses and 1D structures of organic-inorganic hydrid polymers combining M(ClO4)2 (M = Cd, Zn) junctions and the semi-flexible bis-pyridyl ligand 3-pmpmd (N,N′-bis(3-pyridylmethyl)pyromellitic diimide)

Two 1D organic-inorganic coordination polymers, [Cd(3-pmpmd)(CH₃CN)₂(H₂O)₂]_n · 2n(ClO₄)₂ (1) and [Zn(3-pmpmd)_1.5(H₂O)₂]_n · 2n(ClO₄)₂ · nCH₃CN (2), were obtained from M(ClO₄)₂ (M = Cd, Zn) and the semi-flexible 3,3′-N-donor bis-pyridyl ligand 3-pmpmd: 1 has an 1D zigzag framework with 3-pmpmd in the Z_T-mode (anti, trans-) conformation, while 2 has an 1D rod and loop network with 3-pmpmd in both Z_T- and Z_C-mode (anti, cis-) conformations. Results showed that the metal ions could influence the coordination mode of a semi-flexible bis-pyridyl ligand.     

2D coordination polymers of Nd(III) and Gd(III) with the phenoxyacetate ligand

The self-assembly of anionic phenoxyacetate ligands and Nd(III) cations in a 3:1 ratio leads to a 2D {Nd₂(PhOCH₂COO)₆(H₂O)₃ · H₂O}_n coordination polymer 1, which was structurally characterized. The metal centers are bridged by carboxylic groups to form infinite parallel chains separated (19.4 Å) by the π-π and C-H?π-stacked phenoxy groups of the ligands. The thermal dependence of the molar magnetic susceptibility for the isostructural gadolinium polymer 2 has been measured and analyzed according to the analytical expression of an infinite chain of classical spins derived by Fisher. The Gd?Gd interaction is ferromagnetic with a magnitude of 0.015(3) cm⁻¹. Modelling of the field-dependent magnetization at 2 K corroborates this result.     

Structure and luminescence of sodium and lanthanide(III) coordination polymers with pyridine-2,6-dicarboxylic acid

A series of coordination polymers constructed by sodium, lanthanide(III), and pyridine-2,6-dicarboxylate (dipic),NaLn(dipic)₂ · 7H₂O (Ln = Eu, Gd, Tb), have been prepared under a hydrothermal condition. The crystal structures of the three compounds which are isostructual were determined by single-crystal X-ray diffraction. The two-dimensional layers found in the compounds are built up from six-folded {NaO₆} polyhedra and nine-folded {LnN₂O₇} polyhedra, these being edge-shared each other along the c axis and bridged by carboxylate groups of dipic along the b axis, respectively. This two-dimensional framework provides cavities inside the layer and interlayer spaces outside the layer for accommodation of the two dipic molecules coordinated to a lanthanide(III) ions. The dehydrated materials obtained by heating the as-synthesized crystals at 200 °C held their crystal structure, and absorbed the same amounts of water molecules as those of the as-synthesized crystals upon the exposure of 100% relative humidity at room temperature. The Eu and Tb compounds showed strong red and green emissions, respectively, due to an energy transfer from dipic molecules to trivalent emission ions.