Three Lanthanide Coordination Polymers Based on Novel Rigid Tetracarboxylate Ligand:Syntheses,Crystal Structures,and Luminescence Properties

Three lanthanide coordination polymers [Ln（bcpb）0.5（NO3）（DEF）2] （Ln = Y （1）, Tb （2）, Eu （3）, H4bcpb = 2,5-bis（2,4-dicarboxyphenyl） pyridine and DEF = N,N-diethylformamide）） have been solvothermally synthesized under hydrothermal conditions with a novel Hnbcpb ligand and trivalent lanthanide nitrates. Single-crystal X-ray diffraction analysis reveals that compounds 1-3 are isostructural and crystallize in the monoclinic system, space group P21/n. Crystal data for 1： C20H26N409Y, Mr = 555.36, a = 13.022（9）, b = 17.778（12）, c = 10.861（8） A, β= 100.208（3）°, V = 2475（3） A3, Z = 4; Crystal data for 2： C20H26N4OgTb, Mr = 625.37, a = 13.0476（4）, b = 17.8037（7）, c = 10.9398（3） A, β = 100.008（4）°, V = 2496.4（12） A3, Z = 4; Crystal data for 3： C20H26N409Eu, Mr = 618.41, a = 13.055（4）, b = 17.833（5）, c = 10.893（3）A, β = 100.133（4）°, V= 2496.4（12） A3, Z = 4. The compounds were characterized by thermogravimetric analysis （TGA）, IR spectroscopy, and X-ray single-crystal diffraction. Compounds 1-3 all feature 2D networks with -ABAB- fashions. The luminescent properties of compounds 1-3 and free H4bcpb ligand were investigated at room temperature. The results show that the H4bcpb ligand can efficiently transfer energy to the Tb（III） ions, while the energy is not fully transferred from the H4bcpb ligand to the Eu（III） ions.

Mixed-solvothermal Synthesis, Crystal Structure and Luminescence of a New Dinuclear Yttrium(Ⅲ) Coordination Polymer with 1-D Wave-like Infinite Chains

A new dinuclear Y（3＋） coordination polymer{[Y2（H2O）2（C（14）H8O4）3（C（12）H8N2）2]·3 H2O}n （1, C（14）H8 O4 = 2,2＇-biphenyldicarboxylate, phen = 1,10-phenanthroline）, has been obtained by means of a mixed-solvothermal method using ethylene glycol and water as solvent. The compound was characterized by elemental analysis, energy-dispersive X-ray spectroscopy（EDS）, IR spectrum and single-crystal X-ray diffraction. The results reveal that 1 belongs to monoclinic system, space group C2/c with a = 24.249（3）, b = 12.069（48）, c = 22.7304（08） A, β = 113.480（7）°, Z = 4, V = 6102（2） A3, Dc = 1.462 g·cm^-3, F（000） = 2728, μ = 1.968 mm（-1）, the final R = 0.0673, w R = 0.1508 and S = 1.085. Its structure can be regarded as a 1-D coordination polymer constructed by Y^3＋ cations, 2,2A-biphenyldicarboxylate, 1,10-phenanthroline and water molecules. The compound not only contains two kinds of organic ligands, but also exhibits interesting wave-like infinite chains and 18-MR windows with the diameter of 4.070（7）A × 5.326（9）A. The structure is further stabilized by means of O–H…O hydrogen bonds and π-π stacking interactions. Furthermore, the luminescent properties（including emission spectrum, CIE chromaticity coordinate and decay curve） of 1 were also investigated in the solid-state at room temperature.

Syntheses and Structures of Three Novel 1-D Lanthanide-isonicotinate Coordination Polymers

Three novel lanthanide-IN coordination polymers [Ln（IN）3（H2O）2], （Ln = Sm 1, Dy 2, Eu 3; IN = isonicotinate） have been hydrothermally synthesized and characterized by FT-IR spectra, elemental analysis and TG analysis. Single-crystal X-ray diffraction shows that 1, 2 and 3 are isostructural. Crystal data for 1： monoclinic, space group C 2/c, a = 15.8384（14）, b = 14.2662 （12）, c = 9.5073（7） A, β = 97.705（4）°, V = 2128.8（3） A^3, Z = 4, Dc = 1.724 g/cm^3, F（000） = 1084 , μ = 2.806 mm^-1 and R = 0.0226; Crystal data for 2： monoclinic, space group C 2/c, a = 15.7890（3）, b = 14.1356（6）, c = 9.5152（3） A, β= 97.899（2）°, V = 2103.52（12） A^3, Z = 4, Dc = 1.784 g/cm^3, F（000） = 1100, μ = 3.601 mm^-1 and R = 0.0406; Crystal data for 3： monoclinic, space group C 2/c, a = 15.802（5）, b = 14.242（4）, c = 9.513（3） A, β = 97.695（5）°, V = 2121.8（10） A^3, Z = 4, Dc = 1.735 g/cm^3, F（000） = 1088 ,μ = 3.004 mm^-1 and R = 0.0273. In the three compounds, the Ln（Ⅲ） centers are eight-coordinated with antiprismatic geometry. The Ln（IN）3（H2O）2 unit connects mutually to form a one-dimensional double zigzag chain via isonicotinate oxygen bridging. The infinite chains are further linked by inter-chain hydrogen-bonding to form a three-dimensional supramolecular network.

Syntheses,Crystal Structures and Luminescent Properties of Two Lanthanide Coordination Polymers Based on Bifunctional Ligand

Two lanthanide coordination polymers, [Eu（HL）（L）（H2O）2]n（1） and [Tb（H0.5L）2]n（2）, based on bifunctional 5-（1H-imidazol-1-yl） isophthalic acid（H2L）, are hydrothermally synthesized and characterized by both single-crystal and powder X-ray diffraction analyses, and FT-IR. In compound 1, the basic inorganic building unit of the coordination network is the dinuclear [Eu2（COO）6] cluster. Each [Eu2（COO）6] cluster connects four HL^- ligands and each HLligand links two [Eu2（COO）6] clusters, resulting in a 2D coordination layer. The adjacent 2 D layers are further connected via neighboring inter-layer hydrogen bonds to give a 3D supramolecular structure. In compound 2, the Tb^3＋ is coordinated to six oxygen atoms. Each Tb^3＋ ion connects six ligands and each ligand links three Tb^3＋ ions, leading to a 3D coordination polymeric network which exhibits remarkably high thermal stability up to 500℃. Furthermore, due to the successful incorporation of Tb^3＋, compound 2 displays characteristic luminescent emission in the solid state at room temperature. The combination of high thermal stability and fluorescent property of compound 2 would make it as a promising light-emitting material.

A Heterometallic Cu(Ⅰ)-Sr(Ⅱ) Coordination Polymer Based on Isonicotinic Acid Ligand: Synthesis, Crystal Structure, Luminescence and Photocatalytic Performance for Methylene Blue Degradation

Presented here is a new heterometallic Cu(I)-Sr(Ⅱ) coordination polymer, [Cu(3)Sr_2(isonic)_5 Br_2(H_2O)_3]n·n(H_2O)(1, Hisonic = isonicotinic acid), has been synthesized via the hydrothermal reactions of CuBr, Sr(NO_3)_2 and isonicotinic acid. The crystal structure is of triclinic system, space group P1 with a = 7.111(2), b = 14.934(4), c = 18.0255(11) ?, α = 83.137(15), β = 87.155(15), γ = 79.75(2)°, V = 1869.4(8) ?~3, C_(30)H_(29)Br_2Cu(3)N_5O_(14)Sr_2, Mr = 1209.27, Z = 2, Dc = 2.148 g/cm^3, F(000) = 1178, μ = 6.725 mm^(-1), R = 0.0500 and wR = 0.1008 for 4688 observed reflections(I > 2s(I)). Single-crystal X-ray diffraction analysis revealed that compound 1 features a 3 D heterometallic framework stabilized by bifunctional isonic ligands. In addition, the luminescent and photocatalytic properties of compound 1 were also investigated at room temperature.

A One-dimensional Manganese(Ⅱ) Coordination Polymer with 4'-Hydroxybiphenyl-4-carboxylate as the Single Ligand:Synthesis,Crystal Structure and Luminescence

A new 1D coordination polymer,{[Mn2（4＇,4-hbc）4（4＇,4-Hhbc）2（H2O）]·H2O}n（4＇,4-Hhbc=4＇-hydroxyl-biphenyl-4-carboxylic acid）,has been hydrothermally synthesized and struc-turally characterized by elemental analysis,IR spectroscopy and single-crystal X-ray diffraction.The crystal belongs to the monoclinic system,space group C2/c with a=52.421（10）,b=7.5388（15）,c=16.478（3）,β=106.12（3）°,V=6256（2）3,Z=4,C78H62Mn2O21,Mr=1445.16,Dc=1.534g/cm3,μ（MoKα）=0.490mm-1,F（000）=2992,R=0.0764 and wR=0.2006 for 2984 observed reflections with I2σ（I）.X-ray diffraction analyses reveal that the title compound is a one-dimensional infinite chain,in which the MnⅡ atom adopts a distorted octahedral geometry coordinated by four 4＇,4-hbc ligands,one 4＇,4-Hhbc ligand and one water molecule.Furthermore,the luminescent property of title compound was investigated.

Three New Lanthanide Coordination Polymers Constructed from 2,6-Bis(pyrazin-2-yl)pyridine-4-carboxylate: Syntheses, Structures and Luminescence

Three new lanthanide coordination polymers[Ln(bppc)2(suc)0.5(H2O)]n·nH2O(Ln=Eu(1),Ln=Dy(2),Ln=Tb(3),Hbppc=2,6-bis(pyrazin-2-yl)pyridine-4-carboxylate,H2suc=succinic acid)have been hydrothermally synthesized and structurally characterized.These compounds are isostructural and crystallize in triclinic P1 space group.The Ln(Ⅲ)ions are eightcoordinated with dodecahedral coordination geometry.Ln(Ⅲ)cations are linked by carboxylate groups from(bppc)-ligands to form one-dimensional ring chains,which are further connected by the carboxylate groups of(bppc)-and(suc)2-ligands to extend a 2D layer structure.These coordination polymers display the characteristic emission bands of Ln(Ⅲ)ions in the solid state.

Synthesis, Structure and Luminescent Property of an Europium(Ⅲ) Coordination Polymer

A novel europium（Ⅲ） coordination polymer, [Eu3（pydc）3（SO4）（H2O）5（ox）0.5]·3H2O（1, H2ox = oxalic acid, H2 pydc = pyridine-2,6-dicarboxylic acid）, has been synthesized hydrothermally from the self-assembly of lanthanide ions（Eu3＋） with the flexible oxalic acid and the rigid pyridine-2,6-dicarboxylic acid ligands, respectively. It crystallizes in the triclinic system, space group P1 with a = 11.225（4）, b = 12.390（5）, c = 13.752（5）A, α = 89.228（7）, β = 71.142（6）, γ = 75.552（6）°, Dc = 2.317 g/cm^3, μ = 5.480 mm^-1, F（000） = 1150, Z = 2, the final R = 0.0351 and w R = 0.0949 for 8782 observed reflections with I 〉 2σ（I）. Structural analysis reveals that complex 1 exhibits a three-dimensional metal-organic framework via π-π stacking interactions. In addition, complex 1 displays a red fluorescence emission in the solid state at room temperature, which corresponds to the 5D0 → 7F2 transition of Eu3＋ ions.

Ionothermal Synthesis,Structure and Luminescent Properties of a New 2-D Bismuth(Ⅲ) Coordination Polymer with(6,5)-Connected Topological Sheet

A new 2-D Bi（3＋） coordination polymer {Bi4（μ3-O）2（μ4-O）2（C7H3NO4）2}n（1,C7H3NO4 = pyridine-2,6-dicarboxylate） containing（6,5）-connected topological sheet with the Schl？fli symbol of（4~4·6~3·8~4·12~4）（4~5·6~4·8） has been synthesized by an ionothermal method using the ionic liquid 1-ethyl-3-methylimidazolium bromide（[Emim]Br） as solvent,and characterized by C,H and N elemental analysis,energy-dispersive X-ray spectroscopy（EDS）,infrared spectrum（IR spectrum） and single-crystal X-ray diffraction.The results indicate that 1 belongs to the monoclinic system,space group P21/n with a = 13.766（7）,b = 4.142（2）,c = 16.439（8） ？,β = 99.099（9）°,Z = 2,V = 925.6（8） ？~3,Dc = 4.414 g·cm^（-3）,F（000） = 1064,μ = 37.985 mm-1,the final R = 0.0326,wR = 0.0727 and S = 1.022.The molecular structural units [Bi4（μ3-O）2（μ4-O）2（C7H3NO4）2] are connected to each other via bridging O atoms,extending into an interesting 2-D layered structure.These resulting layers are further assembled by weak C-H…O hydrogen bonds into a 3-D supramolecular architecture.Moreover,its thermal stability and the luminescent properties have been also studied.

Hydrothermal Synthesis, Crystal Structure and Photoluminescent Property of a Zinc(II) Coordination Polymer Assembled by Phthalate and 4,4′-Bipyridine

A metal-organic coordination polymer {[Zn（Pht）（4,4＇-bipy）（H2O）2]·2H2O}n （Pht = phthalate, 4,4＇-bipy = 4,4＇-bipyridine） 1 has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, fluorescence spectrum and single-crystal X-ray diffraction. Yellow crystals crystallize in the monoclinic system, space group P2/n, a = 7.6346（14）, b = 11.316（2）, c = 10.8133（19） ,A, β = 92.A.A,A.（3）°, V = 933.3（3） A^3, C18H20N2O8Zn, Mr = 457.73, Dc = 1.629 g/cm^3, F（000） = 472, Z = 2,μ（MoKa） = 1.367 mm^-1, the final R = 0.0323 and wR = 0.0821 for 1859 observed reflections （Ⅰ〉 2σ（Ⅰ））. The structure of 1 exhibits a two-dimensional bilayer framework formed by hydrogen bonding interactions. Furthermore, 1 shows yellow photoluminescent property at room temperature.

Synthesis,Crystal Structure,and Luminescence of a 1D Chain Cd(Ⅱ) Polymerwith 3,3＇,5,5＇-Benzene-1,3-biyl-tetrabenzoic Acid

A new Cd（Ⅱ） coordination polymer, [Cd（H2btb）（bpy）]n（1, H4btb = 3,3？,5,5？-benzene-1,3-biyl-tetrabenzoic acid, bpy = 2,2？-bipyridine）, has been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric（TG） analyses and single-crystal X-ray diffraction techniques. Complex 1 belongs to monoclinic system, C2/c space group. In 1, two carboxylate groups of the H4btb ligand adopt bidentate chelating and μ2-η^1：η^1 coordination modes, respectively, bridging the Cd（Ⅱ） atoms to generate a 1D polymeric ribbon. In addition, the photoluminescence property of complex 1 has also been studied.

Synthesis,Structure and Luminescent Properties of a Two-dimensional Cobalt(Ⅱ) Coordination Polymer Based on 2-Thiobarbituric Acid

A two-dimensional coordination polymer [Co（H2tba）2（DMF）2]n 1 （H2tba = 2-thiobarbituric acid anion, DMF = N,N-dimethylformamide） has been synthesized by CoCl2？6H2O with the 2-thiobarbituric acid ligands under solvothermal conditions. Compound 1 was further characterized by FTIR, elemental analysis, TGA and powder XRD techniques. Single-crystal X-ray diffraction studies revealed that the title compound crystallizes in the monoclinic space group Pbca with a = 12.5948（12）, b = 11.4269（11）, c = 14.8939（15） , V = 2143.5（4） ？3, Z = 4, Dc = 1.523 g·cm-3, F（000） = 1012, μ = 1.038 mm-1, R = 0.0358 and wR2 = 0.0888 （I 〉 2σ（I））. Single-crystal X-ray diffraction analysis reveals that 1 is the first two-dimensional noninterpenetrating （4, 4） net coordination polymer based on the 2-thiobarbituric acid. Coordination polymer 1 exhibits two luminescent emission spectra at 477 and 489 nm with the excitation peak at 273 nm.

Synthesis of Lanthanide Coordination Polymers with Benzophenone-4,4-dicarboxylate: Effect of Lanthanide Contraction on Structures

Four lanthanide coordination polymers with benzophenone-4,4-dicarboxylic acid (H2bpndc) and 1,10-phenan- throline (phen), [Ln2(bpndc)3(phen)] (Ln=La (1), Pr (2) and Tb (3)), [Yb(bpndc)1.5(phen)]0.5H2O (4) were ob-tained through solvothermal synthesis. The crystallographic data show that 1, 2, and 3 are isostructural, the Ln(III) ions in 1, 2 and 3 are all eight- and ten-coordinated, respectively, and thus the Ln(III) ions are connected by bpndc ligands, resulting in an interpenetrating 3D structure. While in 4, the Yb(III) ions are eight-coordinated and con-nected by bpndc ligands into a 3D structure with 1D rhombic channels, which result from the effect of lanthanide contraction from La(III) to Yb(III) ions, and the bpndc ligands in 1, 2, 3, and 4 display three types of coordination modes.

Synthesis,structure and property of serial p-carboxylphenoxyacetate-lanthanide coordination polymers

Four novel lanthanide-based coordination polymers, [Ln(PBDC)(HPBDC)(H2O)3] (H2PBDC=p-carboxylphenoxyacetate; Ln = La (1), Pr (2), Nd (3)) and [La2(PBDC)3(H2O)4] (4), have been prepared through hydrothermal synthetic methods. Compounds 1―3 are isomorphous and exhibit one-dimensional (1D) chain-like motifs, while compound 4 features a complicated three-dimensional (3D) architecture, which is designed and synthesized based on the inspiration from the structure characterization of compound 1. Under the similar reaction conditions, the carboxyl in compound 1 may be further deprotonated by adding the organic base of 2,2'-bipyridine. This subtle change caused a significant difference in the structures, from 1D chain of 1 to a 3D structure of 4. In addition, IR, UV-Vis, TGA and magenetic properties are also investigated in this paper.

Cadmium(II)-1,4-phenylenediacetate Complex with Green Luminescence

The title complex, formulated as {[Cd（pda）（phen）]·3H2O}, 1 （pda = 1,4-phenylenediacetate, phen = 1,10′-phenanthroline）, has been hydrothermally synthesized and determimned by X-ray crystallography. Crystallographic data： triclinic, space group P1^-, a = 10.375 （7）, b = 10.435（1）, c = 12.040（1） A.α = 68.503（1）, ,β= 86.371（1）, γ= 66.231（1）°, Mr = 538.82, V = 1104.5（8） ,A^3, Z = 2, Dc = 1.620 g/cm^3,μ = 1.035 mm^-1, F（000） = 544, the final R = 0.0380 and wR = 0.0985 （w = 1/[σ^2（F0^2） ＋ （0.0559P）^2 ＋ 1.5319P], where P = （F0^2＋ 2Fc^2）/3） based on 3444 observed reflections with I 〉2σ（I）. Complex 1 features a two-dimensional layer. Fluorescent analysis reveals that it exhibits intense green luminescence with the maximum at around 516 nm.

A Y(Ⅲ)-organic Coordination Polymer Constructed from 2-(Pyridine-4-yl)-1H-imidazole-4,5-dicarboxylate and Oxalate Ligands: Structure and Luminescent Property

A novel compound, {[Y（HPIDC）（OX）1/2（H2O）]·2H2O}n （1, H3PIDC = 2-（pyridin-4- yl）-1H-imidazole-4,5-dicarboxylic acid, H2OX = oxalic acid）, has been synthesized under hydrothermal conditions and characterized by thermal analysis （TGA）, powder X-ray diffraction （PXRD）, and single-crystal X-ray diffraction. Complex 1 crystallizes in monoclinic space group P21/c with a = 8.342（8）, b = 14.61（1）, c = 11.487（1）, β = 90.78（9）°, V = 1400.4（2）3, Z = 4, C11H11N3O9Y, Mr = 418.14, Dc = 1.983 g/cm3, F（000） = 836, Rint = 0.0509, T = 293（2） K, μ = 4.240 mm-1, the final R = 0.0477 and wR = 0.1125 for 2770 observed reflections with I 2σ（I）. Compound 1 exhibits a 3D framework and generates the 1D open channels filled with free water molecules. The structure of 1 can be rationalized as a diamondoid network when the atom yttrium is regarded as a 4-connected node linking four surrounding yttrium atoms. The luminescent property of compound 1 is also investigated.

Synthesis and Crystal Structure of a New Zinc(Ⅱ)Coordination Polymer Assembled by 4-Nitrophthalic Acid and Bis(imidazol)Ligands

A new complex [Zn（4-nph）（bib）]（2n）·nH2O（1） has been obtained by the reaction of metal（Zn（Ⅱ））,1,4-bis（imidazol-1-yl）-butane（bib） with 4-nitrophthalic acid（4-H（2nph））.The crystal structure of 1 has been determined by single-crystal X-ray diffraction analysis.Compound 1 is of triclinic system,space group P1 with a = 10.3251,b = 12.4503,c = 16.6497 A,α = 88.487（3）,β = 72.529（3）,γ = 79.991（3）°,V = 2009.8（5）A^3 and Mr = 945.47.Complex 1 shows a three-dimensional（3 D） framework.Moreover,through intermolecular hydrogen bonds,compound 1 is assembled into a supramolecular structure.The thermal stability and luminescent properties of 1 are also investigated.

Hydrothermal Synthesis, Crystal Structure and Photoluminescent Property of a New Isophthalate- bridged Zinc(II) Polymer with One-dimensional Chain Structure: [Zn(ipt)(im)_2]_(2n)·3nH_2O (ipt = Isophthalate, im = Imidazole)

A new metal-organic coordination polymer [Zn（ipt）（im）2]2n·3nH2O 1 has been obtained by using hydrothermal synthesis and characterized by elemental analysis, IR, TG, fluorescence spectrum and single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group P2（1/n） with a = 10.653（3）, b = 17.891（6）, c = 10.743（4）A^°,β= 117.093（5）°, V= 1822.9（10） A^°3, Mr= 413.65, Dc = 1.507 g/cm^3,/t（MoKa） = 1.390 mm^-1, F（000） = 840, Z = 4, the final R = 0.0444 and wR = 0.1066 for 2434 observed reflections （I〉 2σ（I））. Furthermore, compound 1 shows blue photoluminescent property at room temperature.

Hydrothermal Synthesis and Crystal Structure of a Zinc(II) Polymer with a Two-dimensional Layer Structure: [Zn(pzdc)(phen)]_n·nH_2O

A metal-organic coordination compound formulated as [Zn（pzdc）（phen）]n·nH2O 1 （H2pzdc = pyrazine-2,3-dicarboxylic acid, phen = 1,10-phenanthroline） has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group P21/n with a = 11.607（2）, b = 11.719（2）, c = 13.140（3）A^°, β = 110.707（3）°, V= 1671.9（6）A^°3, C18H12ZnN4O5, Mr= 429.69, De = 1.707 g/cm^3,μ（MoKa） = 1.511 mm^-1, F（000） = 872, Z = 4, the final R = 0.0356 and wR = 0.0853 for 2713 observed reflections （I 〉 2σ（I））. It exhibits an interesting two-dimensional layer structure and shows yellow photoluminescent property at room temperature.

A New Pyridine-3,4-dicarboxylic Acid Bridged Zinc(Ⅱ) Coordination Complex: Crystal Structure,Quantum Chemistry and Luminescence Property

A new 2D metal coordination polymer,[Zn(pydc)(L)(H_(2)O)]n·5nH_(2)O(1,H2pydc=pyridine-3,4-dicarboxylic acid,L=3-(2-pyridyl)pyrazole),was synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction,powder XRD,FT-IR,thermogravimetric,fluorescence spectrum and elemental analysis techniques.Complex 1 belongs to the monoclinic system,P21/c space group,with a=10.707(5),b=14.221(5),c=13.278(5)A,β=102.071(5)°,V=1977.1(14)A^(3) and Z=2.It features a 2D network constructed by pydc2-and L ligand.In addition,the quantum-chemical calculations were accomplished on‘molecular fragments’extracted from the crystal structure of 1 using the PBE0/LANL2DZ method built in Gaussian 16 Program.The calculation values denoted the distinct covalent interaction between the coordinated atoms and Zn(Ⅱ)ion.