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,...     

Syntheses,Crystal Structures,and Magnetic Properties of Mn(Ⅱ) and Co(Ⅱ) Coordination Polymers Constructed from Pyridine-tricarboxylate Ligand

Two coordination polymers, namely {[Mn(HL_1)(phen)]·4H_2O}_n(1) and [Co_2(HL_2)_2(H_2O)_2]_n(2) have been constructed hydrothermally using H_3L_1 and H_3L_2(H_3L_1 = 2-(5-carboxypyridin-2-yl)terephthalic acid, H_3L_2 = 2-(4-carboxypyridin-3-yl)terephthalic acid), phen, MnCl_2×4H_2O and CoCl_2×6H_2O. The products were isolated as stable crystalline solids and were characterized by IR spectroscopy, elemental, thermogravimetric(TGA), powder(PXRD) and single-crystal X-ray diffraction analyses. Compound 1 features a 3D framework structure, which was topologically classified as a trinodal 4,6,6-connected net with the unique topology defined by the point symbol of(3~(10).5.6~4)4(3~(10).6.7~4)2(5.6~2.8~2.9). Compound 2 possesses a 2D metal-organic layer, which was topologically classified as a binodal 4,4-connected layer defined by the point symbol of(4~3.6~2.8). The layers are further extended into a 3D supramolecular framework via hydrogen bonds. The magnetic properties for both compounds were also investigated, indicating antiferromagnetic interactions between the adjacent metal ions.     

Two Coordination Polymers with High Selectivity for Sensing Iron(Ⅲ) Constructed from Bifunctional Ligand

A new ligand [1-{2-(2-pyridyl)-benzo[d]imidazole}-2-(5-hydroxyisophthalic acid) ethane] was used to synthesize cadmium and cobalt based florescent organic frameworks successfully under solvothermal conditions. Single-crystal X-ray crystallography of both complexes as well as their thermal stability and luminescence properties was investigated. Much emphasis was placed on the newly synthesized Cd-complex which shows great sensitivity for the detection of Fe~(3+) ions and could be used as a potential probe to detect the Fe~(3+) ions.     

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.     

Two Coordination Polymers Containing Linear Co(Ⅱ)-Trinuclear and Cu(Ⅱ)-Chain Assembled from 4-Fluorocinnamic Acid and N-Donor Ligand

Two new coordination polymers,named {[Co_3(pfca)_6(phen)_2]·2H_2O}_n(1) and[Cu(pfca)_2(4,4'-bpy)(H_2O)]_n(2)(Hpfca = 4-fluorocinnamic acid and 4,4-bpy = 4,4-bipyridine),were hydrothermally synthesized and characterized by elemental analysis,IR spectroscopy,thermogravimetric analysis(TGA),and single-crystal X-ray diffraction.Complex 1 crystallizes in the triclinic crystal system,space group P_1 with a = 10.939(3),b = 12.430(4),c = 13.815(4) A,α=78.436(3),β= 70.261(3),γ= 80.268(3)°,V= 1721.8(9) A~3,D_c = 1.508 g/cm~3,M_r= 1564.06,Z = 1,F(000) = 799,μ= 0.802 mm~(-1),the final R = 0.0432 and wR = 0.1015 for 13250 observed reflections with I 2σ(I).Complex 2 is of monoclinic system,space group P2\lc with a =15.4985(14),b = 15.8424(14),c = 10.9528(10) A,β= 107.1600(10)°,V= 2569.6(4) A~3,D_c = 1.468g/cm~3,M_r = 568.02,Z = 4,F(000) = 1164,μ= 0.906 mm~(-1),the final R = 0.0371 and wR = 0.0842 for 18183 observed reflections with I 2σ(I).Complex 1 features linear Co(Ⅱ)-trinuclear units,which are assembled into a final 3D supramolecular structure through π…π stacking interactions and F-H weak interactions.Complex 2 consists of 1D polymeric Cu(Ⅱ)-chains that are further cohered together by extensive H-bonds.     

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'-dipyridyl-amine (4,4'-dpa),namely[Cd2(p-BDC)2(4,4'-dpa)2]n 1 and {[Cd(p-BDC)(4,4'-...     

Structural Diversity and Luminescent Properties of Two Zinc(Ⅱ) Polymers Based on Semirigid N-heterocyclic Ligand

By varying the spacer angles of phenylenediacetic acid, two novel Zn(II) coordination polymers based on semirigid N-heterocyclic ligand 1,4-bis(2-ethylbenzimidazol-1-ylmethyl) benzene, [Zn(beb)0.5(m-phda)]n(1) and {[Zn(beb)(p-phda)]·2H2O}n(2), were synthesized and fully structurally characterized. Polymer 1 exhibits a 2D grid-layer with a 44 topology. Polymer 2 shows a 2D layer with rare meso-helix. In addition, the thermal stability and photoluminescence properties of polymers 1 and 2 have also been investigated.     

Two New Zn(Ⅱ)/Cd(Ⅱ) One-dimensional Coordination Polymers Based on Naphthalimide Dicarboxylic Ligand

The assemble reactions of 5-(1,3-dioxo-~1H-benzo[de]isoquinolin-2(3 H)-yl)isophthalic acid(H_2L) and Zn2+/Cd2+ ions led to two compounds: [ZnL(DMSO)2]?3DMSO(1) and [Cd2 L2(DMSO)4]?DMF(2). 1 and 2 feature 1 D coordination chains. Weak ?-? interactions further connect the 1 D chains into 2D supramolecular networks. Upon grinding, 1 and 2 show increase of quantum efficiencies(34.8 and 45.4 times of increase compared with original samples for the two compounds respectively) and red shift of the emission peaks(45 and 41 nm of shift compared with original samples for the two compounds, respectively). Both indicate the compounds are good mechanoluminescence responsive materials.     

Two Coordination Polymers Constructed by Cd(Ⅱ) and Zn(Ⅱ) with in situ Generated 5-(3-Pyridyl)tetrazolate Ligand:Syntheses,Crystal Structures and Luminescence Properties

Hydrothermal reactions of 3-cyanopyridine and Na N3 with Zn Cl_2 or Cd Cl_2·5/2H_2 O in the presence of 1,4-benzenedicarboxylic acid(H2bdc) yielded two new coordination polymers,{[Zn(3-ptz)(bdc)_(0.5)(H_2O)_2]n·2H_2O}_n(1) and [Cd_2(3-ptz)_2Cl_2]_n(2),based on in situ synthesized 5-(3-pyridyl)tetrazolate(3-ptz-) organic ligand.They have been structurally characterized by elemental analysis(EA),infrared spectroscopy(IR) and single-crystal/powder X-ray diffraction(PXRD).In 1,two Zn(Ⅱ) ions are linked together through two μ_2-(3-ptz-) ligands to form a dimeric unit of [Zn(μ_2-3-ptz)(H_2O)_2]_2~(2+),which is further connected with other equivalent units by μ_2-bdc~(2-)spacers,resulting in an infinite 1D polymeric chain of [Zn_2(3-ptz)_2(H_2O)_2(bdc)]_n,and then strong hydrogen bonding interactions extend these 1D chains into a 3D supramolecular structure.In 2,the Cd(Ⅱ) ions are connected through μ_4-(3-ptz-) ligands and Cl-anions,leading to infinite 2D layers of [Cd_2(3-ptz)Cl_2]_n~(n+),which are further linked by another μ_4-(3-ptz-) pillared ligand to form a 3D layered-pillared framework architecture of [Cd)2(3-ptz))2Cl)2])n.Furthermore,thermal stability of these compounds was measured by thermogravimetric analysis(TGA) and their photoluminescent properties were also investigated in the solid state at room temperature.     

A Manganese(Ⅱ) Coordination Polymer Constructed from Phosphonate Ligand:Synthesis,Crystal Structure and Magnetic Properties

A coordination polymer formulated as[Mn(5-pncH₂)₂H₂O](1,5-pncH₃=5-phosphono-1-naphthalenecarboxylic acid),was hydrothermally synthesized and magnetically characterized.Compound 1 features a three-dimensional structure in which the inorganic chains of[Mn(O-P-O)]_n are cross-linked by the organic groups of phosphonate ligands.Magnetic measurements of 1 indicate that dominant antiferromagnetic interactions are mediated between the Mn^Ⅱ centers.     

Syntheses and Characterizations of Two Manganese(Ⅱ) Coordination Polymers Containing Three-dimensional Interpenetrating Networks Constructed by Mixed Ligands

Two new three-dimensional coordination polymers, namely [Mn(L)(bpdc)]n(1), [Mn(L)0.5(ndc)]n(2)(L = 1,4-bis(2-methylbenzimidazole)butane, H2 bpdc = 4,4?-biphenyldicarboxylic acid, H2 ndc = 2,6-naphthalenedicarboxylic acid) have been successfully synthesized under hydrothermal conditions. Two complexes were characterized by physico-chemical, spectroscopic methods and single-crystal X-ray diffraction. Complex 1 shows a 3D → 3D 5-fold interpenetrated network with a 4-connected uninodal dia topology. Complex 2 possesses a 3D → 3D 3-fold interpenetrating architecture with a binodal(4,5)-connected xah topology. The fluorescence and thermal properties of the title complexes were discussed.     

Syntheses,Structures and Catalytic Properties of Two Mn(Ⅱ) and Cd(Ⅱ) Coordination Polymers through in Situ Ligand Reaction

Two coordination polymers, namely [Mn(μ-Hcpia)(bipy)(H_2O)_2]_n(1) and [Cd_3(μ_3-Hcpia)_2(μ-Hbiim)_2(μ-H_2biim)(H_2O)_2]_n(2), have been constructed hydrothermally using H_2cbia(H_2cbia = 5-(4'-cyanobenzoxy)isophthalic acid), bipy(bipy = 4,4'-bipyridine), H_2biim(H_2biim = 2,2'-biimidazole), and manganese or cadmium chlorides at 160℃. Interestingly, the H_3cpia(H_3cpia = 5-(4'-carboxylphenoxy)isophthalic acid) ligand was generated by in situ hydrolysis of cyano group in H_2cbia. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses(TGA), and single-crystal X-ray diffraction analyses. Both compounds crystallize in the triclinic system, space group P1. Compound 1 discloses a 1D linear chain of the 2C1 topological type. Adjacent chains are assembled into a 2D supramolecular sheet through O–H···O/N hydrogen bonds. Compound 2 features a 3D framework with a 3,4,4 T25 topology. The luminescent and catalytic properties of two compounds were investigated. Compound 1 exhibits a superior catalytic activity in the cyanosilylation at room temperature.     

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.     

Two New Zn(Ⅱ) and Co(Ⅱ) Coordination Polymers Constructed by 4-Bromobenzoic Acid and 1,4-Bis(imidazol-1-yl)-butane: Synthesis,Crystal Structure and Theoretical Calculations

Two new coordination polymers, [Zn(bba)_2(bib)]_(2n)(1) and [Co_(0.5)(bba)(bib)_(0.5)]_(2n)(2)(Hbba = 4-bromobenzoic acid, bib = 1,4-bis(imidazol-1-yl)-butane), have been hydrothermally designed and synthesized, and their structures were determined by elemental analyses, IR spectroscopy, TG, fluorescence spectroscopy, X-ray single-crystal and powder diffraction. Complexes 1 and 2 both belong to the monoclinic system and exhibit one-dimensional zigzag chain-like structure. In addition, we analyzed Natural Bond Orbital(NBO) in using the PBE0/LANL2 DZ method built in Gaussian 03 Program. The calculation results indicated the obvious covalent interaction between the coordinated atoms and Zn(Ⅱ), Co(Ⅱ) ions.     

Syntheses and Crystal Structures of Two Zn(Ⅱ) Coordination Polymers Constructed with 4,4’-(Dihydroxymethylene)dibenzoic Acid

Two new isomorphous metal-organic coordination polymers, [Zn(dhmdb)(2,2'- bpy)]n 1 and [Zn(dhmdb)(1,10-phen)]n 2, have been obtained under hydrothermal reactions from 4,4'-(dihydroxymethylene)dibenzoic acid (H2dhmdb), Zn(NO3)2·6H2O and 2,2'-pyridine or 1,10- phenanthroline, respectively. Compounds 1 and 2 have been characterized by FT-IR spectroscopy, thermal analysis and single-crystal X-ray diffraction. The zigzag chains of 1 and 2 are linked into three-dimensional supramolecular networks by both O-H…O hydrogen bonds and π…π stacking interactions. Crystal data for 1: ZnC25H18N2O6, Mr = 507.78, orthorhombic, space group Pbca, a = 14.031(3), b = 10.826(2), c = 27.343(6), V = 4153.5(14)3, Z = 8, Dc = 1.624 g/cm3, F(000) = 2080, μ = 1.231 mm-1, R = 0.0699 and wR = 0.1829. Crystal data for 2: ZnC27H18N2O6, Mr = 531.80, orthorhombic, space group Pbca, a = 13.796(3), b = 10.809(2), c = 28.612(6), V = 4266.8(15)3, Z = 8, Dc = 1.656 g/cm3, F(000) = 2176, μ = 1.203 mm-1, R = 0.0454 and wR = 0.1399.     

Two Cd(Ⅱ) Coordination Polymers Based on a Flexible Tricarboxylate Ligand: Syntheses,Structures, and Photoluminescence and Catalytic Properties

Studies on the synthesis and design of coordination polymers(CPs) with flexible ligands are of great interest owing to their dynamic structures and promising applications. The title coordination polymers, {[Cd·(HTTTA)·(phen)]·2H_2 O}n(1) and [Cd·(HTTTA)·(phen)]n(2)(H3 TTTA = 2,2',2'-[1,3,5-triazine-2,4,6-triyltris(thio)] tris-acetic acid, phen = 1,10-phenanthroline) have been synthesized and characterized by elemental analysis, IR, powder XRD and single-crystal X-ray diffraction. Complex 1 consists of one CdII ion, one HTTTA2-ligand and one phen co-ligand. The Cd(Ⅱ) metal clusters were bridged by the tridentate HTTTA2-ligands into infinite 1D chains, which are further connected into the 3D architecture by abundant hydrogen bonds. In 2, three carboxyl groups of HTTTA2-ligand show different coordination directions because of the C–S–C flexible bond angle, which leads to different 1D chains of 2. The strong π-π stacking interaction and four C–H···O hydrogen bonds connect the 1D chains into a 3D framework. The solid-state photoluminescence and catalytic properties were studied as well.     

Two Interpenetrated and Polycatenated Zn(Ⅱ) Coordination Polymers: Syntheses,Structures and Luminescent Properties

Two fascinating Zn(II)entangled coordination polymers,[Zn(eoba)(bbi)]_n·nH_2O(1)and[Zn(boba)(bbi)_(1/2)]_n(2),(bbi=1,1?-(1,4-butanediyl)-bis(imidazole),H_2eoba=4,4?-(ethane-1,2-diyldioxy)-dibenzoic acid,H_2boba=4,4?-(butane-1,4-diyldioxy)-dibenzoic acid),were obtained by hydrothermal technology and characterized by elemental analysis,infrared spectrum,thermogravimetric analysis and single-crystal X-ray diffraction.1 is a rare 2D→3D example with a 3-fold parallel interpenetration and polycatenaned architecture.2 features a scarce2D→2D example with a 3-fold parallel interpenetrating network which possesses polyrotaxane and polycatenane characters.Moreover,the luminescent properties of 1 and 2 have been discussed.     

Two Cobalt(Ⅱ) Coordination Polymers Based on Tetrazylphosphonate and Tetrazylphosphonic Acid Ligands

Two cobalt coordination polymers with the same 2D structure have been hydrothermally synthesized based on two bifunctional ligands with tetrazole and phosphonate(phosphonic acid) groups,namely,diethyl 4-(2H-1,2,3,4-tetrazol-5-yl) benzylphosphonate(C_2H_5-L1) and 4-(2H-1,2,3,4-tetrazol-5-yl)benzylphosphonic acid(H_2L2). The structures of the two complexes are characterized by elemental analysis,IR,TGA and X-ray single-crystal/powder diffraction. The pink block crystals of complex [Co(L1)(H_2O)]·H_2O(1) belong to the monoclinic system,space group C2/m with a = 20.8390(11),b = 7.2695(3),c = 10.0156(6) ?,β = 109.773(7)o,V = 1427.80(13) ?~3,Z = 4,D_c = 1.680 mg/cm~(-3),M_r = 361.16,F(000) = 740,R = 0.0316 and wR = 0.0826 for 1702 observed reflections(I 2σ(I)). The purple block crystals of complex [Co(L2)(H_2O)]·2H_2O(2) also belong to the monoclinic system,space group C2/c with a = 25.5382(16),b = 7.3844(3),c = 15.1925(11) ?,β = 124.238(9)o,V = 2368.6(2) ?~3,Z = 8,D_c = 1.969 mg/cm~(-3),M_r = 351.12,F(000) = 1432,R = 0.0475,wR = 0.1617 for 2088 observed reflections(I 2σ(I)). Both the nitrogen atoms of tetrazole group and oxygen atoms of phosphonate(phosphonic acid) groups in the ligands coordinated with the metal cobalt. The magnetic property of complex 1 is also investigated.     

Syntheses,Crystal Structures and Luminescent Properties of Lead(Ⅱ) and Cadmium(Ⅱ) Coordination Polymers Constructed from Biphenyl-2,5,3′-tricarboxylate

Two coordination polymers, namely [Pb(Hbtc)(phen)]n(1) and {[Cd3(btc)2(H2O)4]·2H2O}n(2, H3btc = biphenyl-2,5,3'-tricarboxylic acid, phen = 1,10-phenanthroline), were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a zigzag chain 1D coordination network, which is further extended into a 3D supramolecular architecture via O–H···O hydrogen bonds and π-π packing interactions. Compound 2 features a 3D open framework based on a tricadmium(II) subunit, generating a trinodal 4,4,6-connected net with the 4,4,6T24 topology defined by the point symbol of(44·62)3(46·69)2. Thermal stability and luminescent properties of both compounds were studied and discussed.