A Mn(Ⅱ) Coordination Polymer with the Flexible Tripodal Ligand 1,3,5-Tris-(imidazol-1-ylmethyl)benzene

A new Mn(Ⅱ) coordination polymer {[Mn(timb)2(H2O)2]·(Cl)2·(H2O)2}n(1,timb = 1,3,5-tris-(imidazol-1-ylmethyl)benzene) has been synthesized and characterized by elemental analysis,IR,TG and single-crystal X-ray diffraction.The title compound crystallizes in the triclinic system,space group P1 with a=9.0774(13),b=9.8720(15),c=11.4898(16),α=93.378(3),β= 95.471(3),γ=101.101(3)°,V=1002.6(3)3,Mr=834.67,Dc=1.382 g/cm3,μ(MoKα)=0.517mm-1,F(000)=435,GOF=0.986,Z=1,the final R=0.0506 and wR=0.1139 for 3517 observed reflections I2σ(I).It consists of one-dimensional double stranded chains formed through bridging bidentate timb ligands,and these chains are further connected to yield a 3D supramolecular framework by hydrogen bonding interactions and π…π stacking interactions.     

A Zn(Ⅱ) Coordination Polymer Based on a Flexible Symmetric Multicarboxylate Ligand

A novel coordination polymer, namely [Zn_2(CAPA)(DMA)(H_2O)]_(2n)·n(H_2O)(1,H_4CAPA = 5-(bis(4-carboxybenzyl) amino) isophthalic acid, DMA = N,N-dimethylacetamide) has been synthesized through a solvothermal method and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectra, and thermogravimetric analyses. The crystal structure is of monoclinic, space group P21/n with a = 8.0585(5), b = 18.9733(10), c = 20.2044(14) ?, β = 101.144(7)o, V = 3030.9(3) ?~3, C_(56)H_(54)Zn_4N_4O_(21), M_r = 1378.58, Z = 2). The compound forms a three-dimensional(3D) supramolecular framework by linking adjacent layers via hydrogen bonds and π···π interactions. It is interesting that the crystal structure is much related to the flexibility and configuration of the ligand. In addition, the thermal stability and luminescence properties for the compound have also been investigated.     

A New Zn(Ⅱ) Coordination Polymer Constructed from 1,3,5-Benzenetricarboxylate Ligand Exhibiting Photoluminescence

The title Zn(II) coordination polymer {[Zn_2(BTC)(HBTC)(dpa)(Hdpa)]·3H_2O}_n(1,H_3BTC = 1,3,5-benzenetricarboxylic acid,dpa = 4,4?-dipyridylamine),has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction,powder X-ray diffraction,IR spectroscopy and Fluorescence spectroscopy.Complex 1 belongs to the triclinic system,space group P1,a = 9.9415(4),b = 13.5859(8),c = 15.2987(5) ?,α = 96.301(4),β = 107.944(3),γ = 103.575(4)°,V = 1873.48(14) ?~3,Z = 2,μ = 1.365 mm~(-1),Dc = 1.672 g/cm~3,Mr = 943.44,F(000) = 964,the final R = 0.0314 and wR = 0.0710 with I 2σ(I).Complex 1 displays a two-dimensional bilayer coordination polymer.Complex 1 shows fluorescence in the solid state at room temperature.     

Self-assembly of a Mixed-valence Cu(Ⅰ)/Cu(Ⅱ) Coordination Polymer Derived from a Conformationally Flexible Tripodal Phosphoric Trimide Ligand

Reaction of a tripodal ligand, N,N?,N??-tris(3-pyridinyl) phosphoric trimide(TPPA) and CuBr_2·2H_2O result in the assembly of a new polymeric copper coordination polymer, which was characterized by single-crystal diffraction, infrared spectroscopy and elemental analysis. The polymer crystallizes in the triclinic system, space group P1 with a = 9.0964(5), b = 10.2592, c = 10.5822(8) ?, V = 933.01(9) ?~3, Z = 2, C_(30)H_(24)Br_4Cu_3N_(12)O_2P_2, M_r = 985.02, D_c = 1.753 g/cm~3, F(000) = 4072 and μ(MoKα) = 0.746 mm~(-1). The final R and w R are 0.0588 and 0.1329 for 4260 observed reflections with I 2σ(I). Cu(Ⅰ) is tetrahedrally coordinated and Cu(Ⅱ) center adopts square planar coordination geometry. Because of the flexibility of the TPPA ligands, the pyridyl rings rotate though a certain angle and three pyridyl rings on the same TPPA rotate by about 45° with respect to the central P=O groups. TPPA ligand acts as a tridentate ligand and is coordinated with three metal centers with its pyridyl donors to form a 2D-sheet like structure, and it is further connected by N–H···O and N–H···Br, resulting in a 3D network packing. Oxidation states of the metal center have been determined by bond valence sum calculation.     

A Cd(Ⅱ) Coordination Polymer with cds Topology Constructed by Polycarboxylate and Imidazole-containing Ligand

A new Cd(Ⅱ) coordination polymer,{[Cd(pda)(bimb)]·(H_2O)_(0.5)}_n(1,H_2pda=1,3-phenylenediacetic acid,bimb = 4,4-bis(1-imidazolyl)biphenyl),has been synthesized and characterized by elemental analysis,IR spectroscopy,powder X-ray diffraction(PXRD) analyses and single-crystal X-ray diffraction techniques. Complex 1 shows a 4-connected two-fold interpenetrated three-dimensional(3-D) cds topology. In additional,photoluminescent properties of 1 and its dehydrated product have also been studied.     

A Co(Ⅱ) 3,5-Diaminobenzoate Coordination Polymer

The title compound, [Co(C7N2H7O2)2]n·nH2O 1, was synthesized via the hydrothermal reaction of Co(Oac)2 with 3,5-diaminobenzoic acid and characterized by elemental analysis and infrared spectra. The crystal crystallizes in the monoclinic system, space group P21/c with a =7.456(3), b = 9.972(3), c = 10.391 (3) (A), β= 106.435(2)°, V = 741.0(4) (A)3, Z = 2, C14H16CoN4O5, Mr = 379.24, Dc = 1.700 g/cm3, F(000) = 390 and μ(MoKa) = 1.194 mm-1. The final R = 0.0324 and wR = 0.0886 for 1516 observed reflections with I＞2σ(I) and R = 0.0337 and wR = 0.0899 for all data. X-ray diffraction studies reveal that the title compound has an interesting 3D microporous architecture with guest water molecules inside the channel. Each Co atom, adopting a distorted octahedral geometry, is coordinated by two O atoms from two 3,5-diaminobenzoate ligands and four N atoms from four symmetry-related 3,5-diaminobenzoate ligands.     

A Zn(Ⅱ) 5-Aminoisophthalate Coordination Polymer

The title compound, [Zn(AIP)(4,4-bipy)0.5(H2O)]n·0.75nH2O 1, was synthesized via the hydrothermal reaction of Zn(OAc)2 with 5-aminoisophthalic acid (H2AIP) and characterized by elemental analysis and infrared spectra. The complex crystallizes in monoclinic system, space group P21/c with a = 12.672(1), b = 7.6557(4), c = 16.181(1) (A),β = 109.187(2)o, V = 1482.6(2) (A)3, Z = 1, C52H52N8O23Zn4, Mr = 1418.58, Dc = 1.589 g/cm3, F(000) = 724 and μ(MoKα) = 1.685mm-1. The final R = 0.0702 and wR = 0.1524 for 1847 observed reflections with Ⅰ ＞ 2σ(I), and R = 0.0873 and wR = 0.1664 for all data. X-ray diffraction studies reveal that the title compound has an interesting 2D microporous architecture with guest water molecules inside the channel.     

Synthesis, Structure and Luminescent Property of a Zinc(Ⅱ) Coordination Polymer Incorporating Flexible Cyclohexane-1,2,3,4,5,6-hexacarboxylate Ligand

The hydrothermal reaction of Zn(NO3)2·4H2O, cyclohexane-1,2,3,4,5,6-hexacarboxylic acid hydrate (H6LI·H2O, cis-conformation LI: a,e,a,e,a,e) and 2,2'-bpy yielded a new coordination polymer [Zn2(H2LII)(2,2'-bpy)]·2H2O(trans-conformation LII: e,e,e,e,e,e), which was characterized by single-crystal X-ray diffraction, elemental analysis, IR and XRPD(X-ray powder diffraction). This complex crystallized in the triclinic system, with P1 space group and parameters a=0.66922(5) nm, b=0.97291(8) nm, c=1.22184(9) nm, ...     

A 3D Homochiral Mn(Ⅱ) Coordination Polymer Based on the Ligand 2,2?-(Ethane-1,2-diylbis(oxy)) Dicinnamic Acid

A 3D homochiral coordination polymer [Mn(edca)]n(1) was synthesized from a flexible coupled cinnamic acid ligand, 2,2?-(ethane-1,2-diylbis(oxy)) dicinnamic acid(H_2 edca) and MnCl_2×4 H_2 O under solvothermal conditions. The complex crystallizes in orthorhombic, space group P2_12_12_1 with a = 5.5785(8), b = 13.0393(18), c = 23.133(3) ?, V = 1682.7(4) ?~3, M_r = 407.27, D_c = 1.608 Mg/cm~3, F(000) = 836, Z = 4, the final R = 0.0240 and wR = 0.0590 for 2983 observed reflections(I 2σ(I)). In 1, the edca2+ anions alternately bridge the Mn(Ⅱ) cations to form one-dimensional(1 D) infinite helical chains of [Mn(edca)]n, which are further connected by the ligands generating a three-dimensional(3D) homochiral network. The photoluminescence of 1 was also investigated in solid state at ambient temperature.     

A Luminescent Zn(Ⅱ) Supramolecular Coordination Polymer Constructed from 3,4-Thiophenedicarboxylic Acid and Flexible Benzimidazole-based Connector

A new luminescent coordination polymer [Zn(tdc)(pbim)]n 1(tdc = 3,4-thiophenedicarboxylate, pbim = 1,3-bis(benzimidazol-1ˊ-yl)propane) has been synthesized under hydrothermal conditions. The compound crystallizes in monoclinic system, space group P21/c with a = 8.4840(9), b = 16.4913(17), c = 14.9234(16) A, β = 95.8870(10)°, V = 2077.0(4) A3, Z = 4, Mr = 511.84, Dc = 1.637 Mg/m3, μ = 1.324 mm-1, F(000) = 1048, the final R = 0.0361 and w R = 0.0824 for 3656 observed reflections with I 2(I). Structural analyses reveal that 1 exhibits a onedimensional(1D) double chain, which is further connected into a two-dimensional(2D) supramolecular architecture by π-π stacking interactions. The results indicate that H2 tdc and pbim ligand are effective building blocks in constructing polymers with diverse architecture. Solid state properties for 1, such as infrared spectroscopy, elemental analyses, thermal stability and luminescent property, have also been investigated.     

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.     

A New Luminescent Cd(Ⅱ) Coordination Polymer Constructed by Mixed 1,4-Naphthalenedicarboxylate and N-donor Chelating Ligand

In this work, we synthesized a new two-dimensional Cd(Ⅱ) coordination polymer, [Cd(1,4-NDC)(L)](1), by using mixed 1,4-naphthalenedicarboxylic acid(1,4-H_2NDC) and typical chelating N-donor ligands 2-(2-chloro-6-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline ligand(L). Compound 1 crystallizes in monoclinic, space group P_21/n with a = 12.936(5), b = 15.245(5), c = 13.499(5) ?, β = 105.456(5)o, V = 2565.9(16) ?~3, Z = 4, C_(31)H_(16)CdClFN_4O_4, M_r = 675.33, D_c = 1.748 g/cm~3, F(000) = 1344, μ(MoKa) = 1.011 mm~(-1), R = 0.0350 and wR = 0.0926. In 1, each 1,4-NDC anion bridges three adjacent Cd(Ⅱ) atoms to give a two-dimensional layer structure. The L ligands are attached on both sides of the layer in chelating coordination modes. In addition, the N–H···O hydrogen bond between L and 1,4-NDC further stabilizes the layer structure of 1. Moreover, the solid state luminescent property of 1 was also investigated at room temperature.     

A New Cadmium（Ⅱ） Coordination Polymer Incorporating a 3D Framework with 1D Channels Bridged by Flexible Cyclohexane-1,2,4,5-tetracarboxylate Ligand

The hydrothermal reaction of Cd(OAc)2·2H2O, 4,4'-bpy and cyclohexane-1,2,4,5-tetracarboxylic acid (H4L) yields a three-dimensional (3D) coordination porous framework [Cd2LI(4,4'-bpy)1.5(H2O)2]n·2nH2O, which was characterized by single-crystal X-ray diffraction (MoKα radiation, λ = 0.71073), elemental analysis and IR. This complex crystallizes in the monoclinic system, space group C2/c with a = 25.951(3), b = 11.6618(12), c = 20.046(2) , β = 114.863(2)o, V = 5504.4(10) 3, Z = 8, Dc = 1.900 g/cm3, Mr = 787.30, μ = 1.615 mm-1, F(000) = 3128, the final R = 0.0978 and wR = 0.1780. The structure of the complex is a 3D coordination Cd-carboxylate framework consisting of 1D hexagonal channels along the c-axis filled with the bridging 4,4'-bpy ligands. The 4,4'-bpy ligands with two kinds of conformations are located alternately in the channels through coordination and hydrogen interactions to support the whole porous framework, in which the conformation-flexible cyclohexane-1,2,4,5-tetracarboxylate ligand adopts the I (e,a,a,e) conformation and acts as a pentadentate ligand to connect five Cd(Ⅱ) atoms via the carboxylate groups in different coordination modes.     

A Three-dimensional Cd(Ⅱ) Coordination Polymer with Unique 8-Connected LOMFOI Topology Based on Mixed Flexible N/O Ligands

A new metal-organic framework,{[Cd(DPA)(OBA)]·(H2O)}n(1,DPA = 4,4-dipyridylamine,H2OBA = 4,4-oxybisbenzoic acid),has been synthesized and characterized by elemental analysis,IR and single-crystal X-ray diffraction.Single-crystal X-ray analysis shows that it is a 3-D framework.Complex 1 crystallizes in monoclinic,space group C2/c with a = 21.699(7),b = 12.192(4),c = 17.566(5) ,β = 105.254(5)°,V = 4483.43 3,Z = 8,Dc = 1.653 g/cm3,μ = 1.021 mm-1,F(000) = 2240,the final R = 0.0307,wR = 0.0867(I 2σ(I)).Complex 1 exhibits a rare three-dimensional highly 8-connected LOMFOI topology with a point symbol of {424·64}.Thermogravimetric analysis shows that the decomposition temperature of the host framework of the complex is above 400 ℃.     

Syntheses and Structures of a New Tetrazylphosphonate Ligand and the Coordination Polymer Based on Zn~(Ⅱ)

A novel tetrazylphosphonate ligand, namely ethyl 4-(2-ethyl-2H-1,2,3,4-tetrazol-5-yl) benzylphosphonate(Et-L), was designed and successfully achieved from p-cyano benzyl chloride, based on which a zinc coordination polymer(1) with a 2D layer structure has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, TGA and X-ray single-crystal diffraction. The colorless block crystals of H_2L·H_2O were also obtained under the same hydrothermal conditions, which belongs to monoclinic system, space group P2_1/c with a = 13.3141(7), b = 5.1650(3), c = 21.9839(18) ?, β = 115.307(5)°, V = 1366.69(15) ?~3, Z = 4, D_c = 1.391 mg/cm~(-3), Mr = 349.58, F(000) = 600, R = 0.0748 and wR = 0.1917 for 2392 observed reflections(I 2σ(I)). The colorless block crystals of complex 1([Zn(L)(H_2O)]_n) also belong to monoclinic system, space group P2_1/c with a = 22.7464(10), b = 6.0430(3), c = 9.7704(4) ?, β = 92.525(4)°, V = 1341.70(10) ?~3, Z = 4, D_c = 1.731 mg/cm_(-3), M_r = 349.58, F(000) = 712, R = 0.0596 and wR = 0.1688 for 2357 observed reflections(I 2σ(I)). Only the oxygen atoms of phosphonic group are coordinated with the metal zinc probably because the hydrogen atom of tetrazole has been substituted by ethyl group. Photoluminescence properties of the complex are also investigated.     

Syntheses,Structures and Photocatalytic Degradation Properties of Two Copper(Ⅱ)Coordination Polymers with Flexible Bis(imidazole)Ligand

Two copper(Ⅱ)coordination polymers{[Cu(bib)(nip)]·1.5H2O}n(1)and[Cu2(bib)(glu)2]n(2)(bib= 1,4-bis(2-methyl-imidazol-1-yl)butane,H2nip = 5-nitroisophthalic acid,...     

A New Luminescent Cd(Ⅱ) Coordination Polymer Constructed with 2-(Carboxymethoxy) benzoic Acid

In this work, we synthesized a new Cd(Ⅱ) coordination polymer, [Cd(L)(cmb)H_2O]· H_2O(1), by using mixed 2-(carboxymethoxy)benzoic acid(H2 cmb) and typical chelating N-donor ligands 2-(2-fluoro-6-fluorophenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline ligand(L). 1 crystallizes in monoclinic, space group P21/c with a = 17.6150(8), b = 9.7811(4), c = 18.1603(8) ?, β = 118.9150(10)o, V = 2738.9(2) ?~3, Z = 4, C28 H20 CdF2 N4 O7, Mr = 674.88, Dc = 1.637 g/cm3, F(000) = 1352, μ(Mo Ka) = 0.865 mm–1, R = 0.0643 and w R = 0.1976. In 1, the cmb2– anions link neighboring Cd(Ⅱ) atoms in a bis-chelating mode, yielding a one-dimensional chain structure along the b axis. The L ligands are attached on one side of the chain through chelating the Cd(Ⅱ) atoms, and are stacked with those of an adjacent chain through π-π interactions to generate a one-dimensional double-chain structure. Furthermore, the one-dimensional double-chains are stacked by C–H???π interactions between the carbon atom of L ligand and the benzene ring of cmb2–ligand to give a layer structure. Moreover, the solid state luminescent property of 1 was also investigated at room temperature.     

A New Mn(Ⅱ) Coordination Polymer with a Rare Polyrataxane Topology: Synthesis,Crystal Structure and Luminescent Property

A novel coordination polymer [Mn(bcp)(bib)0.5]n(1, H2 bcp = 1,3-bis(4-carboxyphenoxy)propane and bib = 1,4-bis(imidazol-1-yl)benzene) was synthesized under hydrothermal conditions, and was characterized by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectroscopy and powder X-ray diffraction(PXRD).Complex [Mn(bcp)(bib)0.5]n(1) is of triclinic system, space group P1 with a = 7.320(5), b =11.871(5), c = 13.932(5) ?, α = 111.125(5)°, β = 99.658(5)°, γ = 101.104(5)°, Z = 2, V= 1070.3(9)?3 Mr = 474.34, Dc = 1.472 g/cm3, F(000) = 488, μ = 0.660 mm?1, the final R = 0.0353 and wR =0.0.984 for 4373 observed reflections with I 2?(I). Structure analysis reveals that complex 1 displays a rare 2 D + 2 D → 2 D polyrataxane topology. Moreover, the luminescent property for 1 was investigated at room temperature.