Synthesis and Luminescence Properties of Three High-dimensional Coordination Polymers:Zn(Ⅱ) with Imidazole or Benzimidazole Ligand

A novel 2D coordination polymer [Zn2（bim）4]n（1）（Hbim=benzimidazole） based on dihydrated- [N,N＇-bis（2-aminophenl）-oxalamide]（L1·2H2O） with zinc nitrate has been synthesized. Previously we have synthesized complexes [In：Zn3（im）12]n（2）（Him= imidazole） and [Zn（im）2]n（3） successfully. In complex 1, each Zn（Ⅱ） coordinated with four ligands adopts a distorted tetrahedron coordination mode, and the 2D grid structure is built by the Zn（bim）4 as the secondary building unit（SBU）. The luminescence properties of the three complexes were investigated for the first time. The emissions with maxima for complexes 1, 2 and 3 are at 379, 469 and 392 nm, respectively.

Crystal Structure, Thermal Behavior and Luminescence of a New Copper Coordination Polymer Constructed with 4-(Carboxymethoxy)-benzoic Acid

A new Cu(Ⅱ) coordination polymer, [Cu(L1)(L2)](1), was synthesized under hydrothermal conditions(H_2L1 = 4-(carboxymethoxy)benzoic acid, L2 = 2-(4-fluorophenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline). Crystallographic data for 1: triclinic, space group P1 with a = 9.750(5), b = 10.148(5), c = 12.869(5) ?, α = 104.904(5), β = 102.133(5), γ = 95.219(5)°, V = 1188.7(10) ?~3, Z = 2, C_(28)H_(17)FN_4O_5Cu, Mr = 572.01, D_c = 1.598 g/cm^3, F(000) = 582, μ(MoKa) = 0.977 mm^(-1), R = 0.0474 and w R = 0.1144. The TGA behaviors and luminescence of 1 have been studied in detail. The L1 dianions link neighboring Cu(Ⅱ) atoms in a bis-chelating mode, yielding a one-dimensional chain structure along the b axis. The L2 ligands are attached on one side of the chain through chelating the Cu(Ⅱ) atoms, and are stacked with those of an adjacent chain through π-π interactions, yielding a layer structure. Additionally, the N–H???O hydrogen bonds further stabilize the structure of 1.

Hydrothermal Synthesis, Crystal Structure and Luminescent Property of a New Cd(Ⅱ) Coordination Polymer with Four-fold Interpenetrated dia Topology

A new Cd（II） coordination polymer with 2-nitroterephthalie acid （H2npa） and 1,4- bis（2-methyl-imidazol-l-yl） butane （bib） has been prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction, IR and EA. Complex [Cd（npa）（bib）]n （1） is of orthorhombic system, space group Pcca with a = 16.1750（5）, b = 9.8764（5）, c = 15.5890（3） A, V = 2490.4（2） A3, Z = 4, Mr = 539.82, Dc = 1.440 g/cm3, F（000） = 1088,μ = 0.918 mm-1, the final R = 0.0320 and wR = 0.0775 for 2253 reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that complex 1 displays a four-fold interpenetrated dia topology. Furthermore, the luminescent property for complex 1 is also investigated in solid state at room temperature.

Synthesis, Structure and Luminescent Property of a 2D Cd(Ⅱ) Coordination Polymer Based on Mixed-ligands of 1,3-Bis(imidazol)propane and Pyridine-3,5-dicarboxylic Acid

A new Cd（Ⅱ） coordination polymer, namely, [Cd（1,3-bip）（3,5-pdc）]n （1,3-bip = 1,3-bis（imidazol）propane and 3,5-pdc = pyridine-3,5-dicarboxylic acid） has been synthesized under hydrothermal conditions. Compound 1 was characterized by infrared spectrum, elemental analysis, powder X-ray diffraction （PXRD） and single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/c with a = 1.40178（7）, b = 1.72502（12）, c = 1.41635（6） ran, β = 92.653（4）°, V = 3.4212（3） nm3, Z = 4, C16HIsCdNsO4, Mr = 453.73, Dc = 1.762 g/cm3, F（000） = 1808,μ = 1.310 mm1, R = 0.0899 and wR = 0.1945. In compound 1, each 3,5-pdc ligand links three Cd（lI） ions and each Cd（Ⅱ） attaches to bip ligands to form a complicated 2D double-layer structure. In addition, the thermal stability and luminescent property of 1 have been studied in the solid state at room temperature.

Synthesis, Crystal Structure and Photoluminescence of a Zn(Ⅱ) Coordination Polymer Derived from 1,1'-Biphenyl-2,2',6,6'-tetracarboxylic Acid

A new polymeric znic（II） coordination polymer, [Zn2（bptc）·（H2O）4]n·nC H3 OH 1, was synthesized by the hydrothermal reaction of Zn（NO3）2·6H2O with 1,1＇-biphenyl-2,2＇,6,6＇-tetracarboxylic acid（H4bptc） and structurally characterized by single-crystal diffraction, IR and elemental analysis. The polymer crystallizes in the orthorhombic system, space group Pnna with a = 13.411（1）, b = 16.418（2）, c = 9.178（7）, V = 2025.2（3） 3, Z = 4, C17H14O13Zn2, Mr = 557.06, Dc = 1.827 g/cm3, F（000） = 1120, μ（MoK α） = 2.439 mm-1. The final R and wR are 0.0548 and 0.1691 for 1279 observed reflections with I 2（I）. In this compound, the bptc4- anion adopts monodentate bridging coordination modes connecting the zinc（II） ions to form a 1D chain structure, which furnishes a 2D supramolecular architecture through hydrogen bonding interactions formed by carboxylic oxygen atoms of bpdc, oxygen atoms of crystalline methanol and water molecules. Complex 1 displays an emissive maximum at 435 nm in the solid state at room temperature.

A Two-dimensional Anthracene-9,10-dicarboxylate Zinc(Ⅱ) Coordination Polymer Based on Binuclear [Zn_2Cl_2] Nodes: Synthesis, Characterization and Luminescent Properties

A two-dimensional（2D） 44 topological ZnⅡ coordination polymer {[Zn2Cl2（L）（4bpy）2]}∞（H2L = anthracene-9,10-dicarboxylic acid, 4bpy = 4,4ˊ-bipyridine） based on binuclear [Zn2Cl2] nodes has been synthesized and characterized by IR, elemental analysis, X-ray powder diffraction and single-crystal X-ray diffraction analysis. Moreover, the luminescent properties of the correspon- ding compound have been briefly investigated.

Synthesis and Characterization of a New 3D Pillared Bilayer Cd(Ⅱ) Coordination Polymer Based on 6,6?-Dinitro-2,2?,4,4?-biphenyltetracarboxylic Acid

A new 3D Cd（II） coordination polymer, [Cd2L（dpe）]n （1, HaL = 6,6＂-dinitro-2,2＂,4, 4＂-biphenyltetracarboxylic acid, dpe = 1,2-di（4-pyridyl）ethylene）, has been synthesized using the hydrothermal method and characterized by single-crystal X-ray diffraction, elemental analysis, IR, thermogravimetric analysis, and photoluminescent analysis. Complex 1 crystallizes in the monoclinic system, space group C2/c with a = 8.0006（15）, b = 23.900（5）, c = 14.836（3） A, fl = 95.723（3）°, V = 2822.7（10） A3, Z = 8, Dc = 1.937 Mg.m3, p = 1.581 mm-1, F（000） = 1608, the final R = 0.0231 and wR = 0.0629 for 2239 observed reflections with I 〉 2a（/）. Complex 1 is a 3D pillared bilayer （4,5,7）-connected net with the Schlfli symbol of （4^14·6^7） （4^2·6^5·8^3） （4^4·6^2） topology. The photoluminescent property of 1 is also investigated.

Synthesis, Crystal Structure and I2 Capture of a Cd(Ⅱ) Coordination Polymer Based on a Linear Bipyridyl Benzene Ligand

A new complex with formula [Cd（3-pbpmb）2 I2]n 1（3-pbpmb = 1,4-bis（pyridine-3-ylmethoxy）benzene）, has been solvothermally synthesized and characterized. The crystal belongs to monoclinic system, space group P21/n with a = 8.2905（17）, b = 16.078（3）, c = 13.213（3）A, β = 99.44（3）°, Mr = 950.86, V = 1737.3（6） A^3, Z = 2, Dc = 1.818 g/cm^3, F（000） = 924, m = 2.450 mm（-1）, the final R = 0.0198 and w R = 0.0467 for 3053 observed reflections（I ＆gt; 2σ（I））. The Cd（Ⅱ） ion is coordinated by four N atoms of four 3-pbpmb ligands and two iodine ions to furnish a distorted octahedral coordination geometry. The Cd（Ⅱ） ion and its own symmetry-related ions are bridged by N atoms from two 3-pbpmb ligands to generate a ＂zigzag＂ 1-D chain coordination polymer. These 1D chains are further connected into a three-dimensional（3D） framework by C–H×××pinteractions and intermolecular C–H×××I hydrogen bond. Interestingly, 1 displays efficient sorption of molecular iodine gas（up to 111 wt%）, but invalid sorption of molecular water gas.

Synthesis and Crystal Structure of a Cadmium(Ⅱ) Coordination Polymer:[Cd_2Cl_4(bpme)]_n·n(2H_2O)

A novel coordination polymer, [Cd2Cl4（bpme）]n·n（H2O） （1, bpme=2,5-bis（be-nzoimidazol-2-yl）pyrazine）, has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction. The crystal of the complex belongs to the triclinic system, space group P , with a=7.0737（9）, b=8.7886（11）, c=9.4561（12） , α=105.3580（10）, β=94.981（2）, γ=96.879（2）°, V=558.46（12） 3, Mr=714.97, Z=1, F（000）=346, Dc=2.126 g/cm3, μ=2.412 mm-1, T=296（2） K, S=1.057, R=0.0533 and wR=0.1480. According to the structural analysis, the Cd（Ⅱ） ion adopts a slightly distorted six-coordinated octahedral geometry. The Cd（Ⅱ） atoms are bridged by four Cl atoms along the a direction, forming infinite straight chains which are further constructed to generate 2D network layer structures through the μ4-N bpme ligand in the b direction, and such 2D network layer structures finally form a novel three-dimensional infinite supramolecular framework through weak π-π stacking between two network layers and hydrogen bonds.

Crystal Structure and Luminescent Properties of a Zn(Ⅱ) Coordination Polymer Assembled by Mixed-ligand

A Zn（Ⅱ） coordination polymer [Zn（NIP）（3,3＇-bpt）].H20 （1, NIP = 5-nitroisophtha- late, 3,3＂-bpt = 1H-3,5-bis（3-pyridyl）-l,2,4-triazolate） has been synthesized by the hydrothermal reaction at 140 ℃ and structurally characterized by IR spectroscopy, X-ray diffraction, thermal analysis, single-crystal X-ray diffraction and luminescent properties. In complex 1, the zinc atom is five-coordinated with three carboxylate oxygen atoms from three H2NIP and two nitrogen atoms from two 3,3＇-bpt, respectively, forming a distorted trigonal bipyramidal geometry and showing a 1D chain structure, which is further bridged by NIP to form a 3D supramolecular network via self-assembly of hydrogen bonds.

Syntheses,Structures and Properties for Zn~Ⅱ Coordination Polymers Based on a Functional 4'-(3-Pyridyl)-3,2':6',3''-terpyridine Ligand

Two new Zn~Ⅱ coordination polymers,namely,[Zn L（o-bdc）]n（1） and [Zn L（mbdc）]_n·n H_2O（2）（L = 4？-（3-pyridyl）-3,2？：6？,3？？-terpyridine,H_2（o-bdc） = benzene-1,2-dicarboxylic acid,H_2（m-bdc） = benzene-1,3-dicarboxylic acid）,were synthesized by hydrothermal methods. The crystal structures have been determined by single-crystal X-ray diffraction. Compound 1 crystallizes in monoclinic C2/c space group,with a = 28.016（2）,b = 11.3815（11）,c = 19.8071（17） ？,β = 133.961（2）°,V = 4546.2（7） ？3,Z = 8,Mr = 539.83,Dc = 1.577 Mg/m^3,μ = 1.127 mm-1,F（000） = 2208,the final R = 0.0426 and w R = 0.0986 for 2875 observed reflections with I 〉 2σ（I） and displays a 1D coordination chain. While compound 2 crystallizes in monoclinic C2/c space group,with a = 15.6003（14）,b = 11.9152（11）,c = 26.633（3） ？,β = 94.320（2）°,V = 4936.5（8） ？~3,Z = 4,M_r = 1115.67,Dc = 1.496 Mg/m^3,μ = 1.043 mm^（-1）,F（000） = 2272,the final R = 0.0499 and w R = 0.1342 for 2659 observed reflections with I 〉 2σ（I） and shows a classical 3D cds topological network with point symbol of {65.8}. Furthermore,thermal stability and luminescent properties of 1 and 2 have also been investigated.

A New 2D Zinc(Ⅱ) Coordination Polymer Constructed by Imidazole-4,5-dicarboxylic Acid(H_3IDC) and 1,4-Bis(imidazol-1-ylmethyl)-benzene(bix)

A new 2D Zn（Ⅱ） coordination polymer [Zn（HIDC）（bix）0.5]n（1） was obtained by the hydrothermal reaction of ZnCl2,imidazole-4,5-dicarboxylic acid（H3IDC） and 1,4-bis（imidazol-1-ylmethyl）-benzene（bix） with a 2：2：1 mole ratio.X-ray diffraction crystal structural analysis reveals it crystallizes in monoclinic,space group P21/n with a = 12.125（3）,b = 10.541（3）,c = 12.484（3） ,β = 115.834（4）°,V = 1436.0（6） 3,Mr = 338.60,Z = 4,Dc = 1.566 Mg·m-3,F（000） = 684,μ（MoKα） = 1.730 mm-1,the final R = 0.0439 and wR = 0.0888 for 2101 observed reflections with I ≥ 2σ（I）.In 1,each zinc（Ⅱ） ion is five-coordinated with a slightly distorted trigonal bipy-ramidal coordination geometry,and each μ2-HIDC2-acts as a bridge to bond two neighboring Zn（Ⅱ） ions,leading to a 1D zigzag chain architecture.The adjacent zigzag chains are further linked by μ2-bix to form an infinite 2D network structure.The fluorescence spectrum of 1 exhibits intense emission at 466 nm when excited at 397 nm in solid state at room temperature.

A Novel 6-Connected Self-interpenetrated Zn(Ⅱ) Coordination Polymer Based on 1,4-Bis(2-methylimidazole-3-ium-1-yl)biphenyl and Dicarboxylate Ligand: Synthesis, Crystal Structure and Luminescent Property

A novel coordination polymer {[Zn2（pda）2（bmp）1.5]·2H2O}n（1, H2 pda = 1,4-phenyl enediacetic acid and bmp = 1,4-bis（2-methy limidazol-3-ium-1-yl）biphenyl） was synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectroscopy and powder X-ray diffraction（PXRD）. Complex {[Zn2（pda）2（bmp）1.5]·2H2O}n（1） is of triclinic system, space group P1 with a = 10.132（5）, b = 11.854（5）, c = 18.784（5） A, α = 80.256（5）, β = 75.163（5）, γ = 75.620（5）°, Z = 2, V = 2099.0（15） A3, Mr = 908.54, Dc = 1.437 g/cm^3, F（000） = 938 and μ = 1.206 mm-1. The final R = 0.0541 and wR = 0.1397 for 8017 observed reflections with I 2σ（I）. Complex 1 displays a three-dimensional（3D） self-interpenetrated 6-connected topological net with point symbol（48.67）. Furthermore, the luminescent property of complex 1 was investigated in the solid state at room temperature.

Construction of a Set of Cadmium(Ⅱ) Coordination Polymers with Atza and 2,2′-Bipy or 1,10-Phen Ligands (Atza=5-Aminotetrazole-1-acetato Anion)

Reactions of CdX2（X=NO3-, ClO4-） with Hatza （atza=5-aminotetrazole-1-acetato anion） and 2,2′-bipyridine （2,2′-bipy） or 1,10-phenanthroline （1,10-phen） in a methanol/aqueous solution produced a set of new Cd（Ⅱ） coordination polymers, {[Cd（atza）（H2O）（2,2′-bipy）]ClO4}n （1）, {[Cd（atza）（H2O）（1,10-phen）]ClO4 }n （2）, {[Cd（atza）（H2O）（2,2′-bipy）]NO3}n （3） and {[Cd（atza）2 （1,10-phen）]·0.5H2O}n （4）. Single-crystal X-ray diffraction analysis reveals that each Cd（Ⅱ） ion has a distorted octahedral coordination geometry in 1-4, and the Cd（Ⅱ） ion centers are connected through the tridentate atza bridging ligands to form a 2D layer （1-3） or ID chain （4） structure. The fluorescent properties of 2 and 4 are also discussed.

A New 3D Pb(Ⅱ) Coordination Polymer [Pb(L)]_n Based on a Long Flexible Octane-1,8-dicarboxylic Acid:Crystal Structure and Physical Properties

A new Pb（II）-based coordination polymer, [Pb（L）]n （1）, was hydrothermally synthesized and its structure was determined by single-crystal X-ray diffraction （H2L = octane- 1,8-dicarboxylic acid）. Compound 1 crystallizes in orthorhombic, space group Pnma with a = 32.061（4）, b = 7.2597（8）, c = 4.8084（5） A, V= 1119.2（2） A3, Z = 4, C10H1604Pb, Mr = 407.42, Dc = 2.418 g/cm3, F（000） = 760, μ（MoKa） = 15.066 mm-1, R = 0.0270 and wR = 0.0666. In 1, each Pb（II） cation is coordinated by six carboxylate oxygen atoms from four L2- anions. Each L2- anion bridges three Pb（ll） atoms in a μ3：η2：η1：η1 mode to form a 3D framework. The structure of 1 was characterized by IR spectrum and thermogravimetric analysis. Moreover, solid state luminescent property of 1 was also investigated.

Cd/Mn(Ⅱ) Complexes with Heterocyclic Substituted 1,2,4-Triazole Ligands：Syntheses,Crystal Structures,and Luminescence Properties

Based on a 3-（pyridine-2-yl）-4H-1,2,4-triazole ligand（Hpytr）, one 2D Cd（Ⅱ） coordination polymer [Cd I（pytr）]n（1） and one 2D Mn（Ⅱ） coordination polymer [Mn（N3）（pytr）（H2O）]n（2） have been synthesized and characterized by X-ray crystallography, elemental analysis, and fluorescence spectroscopy. 1 shows a layer coordination architecture linked by pytr ligand, and the Cd（Ⅱ） centers display slightly distorted square pyramid coordination geometries. Complex 2 shows a 2D pillared-layer coordination architecture bridged by N3-and pytr, and the Mn（Ⅱ） centers display slightly distorted octahedral geometries. The luminescent properties of 1 and the PXRD and thermal stability of complexes 1 and 2 were measured briefly.

Syntheses,Structures and Characterizations of Two New Zinc(Ⅱ) Coordination Polymers Constructed from 3-(1H-Pyrazol-4-yl)-5-(pyridin-2-yl)-1,2,4-triazole and Different Carboxylate Ligands

Two new zinc（Ⅱ） coordination polymers, [Zn（ph）（H2 L）·H2O]2 n（1） and [Zn（ip）（H2 L）-（H2O）]n（2）（H2 ph = phthalic acid, H2 ip = isophthalic acid, H2L = 3-（1 H-pyrazol-4-yl）-5-（pyridin-2-yl）-1,2,4-triazole）, have been successfully synthesized via hydrothermal reaction. It has been structurally characterized by X-ray single-crystal analysis, IR spectra, fluorescence spectroscopy and thermogravimetry analysis. The single-crystal X-ray diffraction studies reveal that compounds 1 and 2 both exhibit 1D chain structures, and assemble into 2D and 3D supermolecules through hydrogen bonds or π-π interactions. Moreover, the thermal stability and luminescent properties of compounds 1 and 2 were also studied.

Two temperature-dependent 2D heterometallic Cd(Ⅱ)-Dy(Ⅲ)coordination polymers exhibiting slow magnetic relaxation and luminescence properties

Two unique two-dimensional(2D)Cd(Ⅱ)-Dy(Ⅲ)heterometallic coordination polymers,{[DyCd(HPMA)(PMA)_(2)(H_(2)O)_(4)]·2H_(2)O}_n(1)and[DyCd(PAA)(PMA)_(2)(H_(2)O)_(3)]_(n)(2,PAA^(-)=phenylacetate),were prepared successfully based on the phenylmalonic acid(H_(2)PMA).The construction of two polymers is sensitive to the reaction temperature and can be synthesized directionally at room temperature and 90℃,respectively.Complexes 1 and 2 display 2D layer structures that include dinuclear[Dy_(2)]cluster node and Dy(Ⅲ)-based 1D zigzag chain motif severally.The Dy(Ⅲ)-based units in two structures both are spaced well with the adjacent ones by the diamagnetic Cd(Ⅱ)-based moieties.The magnetic studies reveal that 1 and 2both display slow magnetic relaxation with temperature-dependent relaxation peaks producing an effective energy barrier(Δτ)of 74.5 and 32.1 K,separately.Furthermore,the solid-state photophysical properties of 1 and 2 show strong characteristic luminescent emissions of Dy(Ⅲ)ion in the visible region.

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.

Temperature-controlled Structural Diversity of Two Cd(Ⅱ) Coordination Polymers Based on the Dicarboxylate Ligand

Two new 3-D Cd(Ⅱ) coordination polymers with p-phthalic acid (p-BDC) and 4,4′-dipyridylamine (4,4′-dpa),namely[Cd_(2)(p-BDC)_(2)(4,4′-dpa)_(2)]_(n) 1 and{[Cd(p-BDC)(4,4′-dpa)(H_(2)O)]·4H_(2)O}_(n) 2 were successfully synthesized under hydrothermal conditions at 120 and 140℃.They were characterized by single-crystal X-ray diffraction,IR,PXRD and TGA.It was further characterized by Hirshfeld surface (HS)analysis for complex 2.The luminescent properties of the complexes have also been investigated.