A Novel 3D Twofold Zn(Ⅱ) Coordination Polymer Constructed by Mixed Flexible Ligands: Synthesis,Crystal Structure and Fluorescence Property

A new Zn(Ⅱ) coordination polymer, {[Zn(1,3-bip)(oba)]·0.5H_2O}n(1),1,3-bip =1,3-bis(imidazole)propane, H_2oba=4,4?-oxybis(benzoate)), have been synthesized and characterized by single-crystal X-ray diffraction, powder XRD, FTIR, TGA and elemental analysis techniques. The single-crystal X-ray diffraction reveals that complex 1 shows a 3D→3D twofold interpenetrating network that can be described as a 4-connected uninodal net with(65.8) topology. In addition, the photoluminescence property of complex 1 was also investigated at room temperature.     

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 Tetranuclear Co(Ⅱ) Coordination Cluster with Thienyl-based Quinolinate Ligand and Nitrate Ligands:Syntheses,Structure and Magnetic Properties

One novel Co(Ⅱ) coordination polymer, namely [Co_4(L)_6(NO_3)_2](1) was prepared by solvothermal reactions of Co(NO3)2 with a(E)-2-[2-(3-thienyl)ethenyl]-8-quinolinol ligand(HL), which has been determined by single-crystal X-ray diffraction analyses and further characterized by means of elemental analyses, IR spectra, PXRD and thermogravimetric analyses(TGA). The core structure of complex 1 is an incomplete dicubane-like tetranuclear Co(Ⅱ) cluster, which is surrounded by six 8-hydroxy-quinolinate-based ligands and two nitrate ligands. Weak S–O interactions between the thienyl groups and nitrate ligands extend the adjacent tetranuclear Co(Ⅱ) clusters into a supramolecular(4, 4) net structure. Magnetic measurement indicates that the coupling within both molecules is overall antiferromagnetic.     

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(H_2btb)(bpy)]_n(1, H_4btb = 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 H_4btb ligand adopt bidentate chelating and μ_2-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.     

A Zn(Ⅱ) Coordination Polymer Based on a Flexible Polycarboxylate Ligand 5-(4-Hydroxypyridinium-1-ylmethyl)-isophthalic Acid: Synthesis,Structure, and Property

A Zn(Ⅱ) supramolecular coordination polymer, {[Zn_2(L)_2(m-bix)(H_2O)]·6 H_2O}n(1), with an interesting 1 D→2 D polythreading array from a flexible and angular organic aromatic polycarboxylate ligand 5-(4-hydroxypyridinium-1-ylmethyl)isophthalic acid(H2 L), and N-donor ligand 1,3-bis(imidazol-1-ylmethyl)benzene(m-bix), has been obtained under hydrothermal conditions and characterized by elemental analysis, powder X-ray diffraction(PXRD), IR, thermal gravimetric analyses(TGA) and single-crystal X-ray diffraction. In 1, the Zn(Ⅱ) center has two coordination geometries. One exhibits a trigonal bipyramidal coordination sphere, and the other is a tetrahedral geometry; L2-has two different coordination modes, with one connecting three Zn(Ⅱ) ions through two monodentate carboxylate groups and the monodentate hydroxyl group, and the other bridging two Zn(Ⅱ) ions through two carboxylate groups. The L2-anions connect the Zn(Ⅱ) centers forming an infinite 1 D tubular structure. These 1 D tubes are interconnected by the m-bix spacers to form a 2 D framework. Such 2 D layers are further assembled into a 3 D supramolecular network via hydrogen bonds. Meanwhile, the luminescent property of 1 has also been investigated in detail.     

Synthesis and Crystal Structures of Two Di-Cu(Ⅱ) Complexes Based on an Asymmetric Dinucleating Ligand

Two new dicopper(II) complexes [Cu2L(OAc)2](ClO4)·H2O(1) and [Cu2L(BPP)2]-(ClO4)(2) using an asymmetric dinucleating ligand HL and auxiliary ligands such as acetate(OAc) and bisphenyl phosphate(BPP) have been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Complex 1 crystallizes as blue single crystals that belong to the triclinic crystal system and P1 space group, while complex 2 crystallizes in a monoclinic P21/c space group. Single-crystal X-ray diffraction analysis reveals that the two copper ions in complexes 1 and 2 reside within the adjacent ligand compartments and are bridged by the endogenous phenoxo-O from ligand L and the introduction of two desired exogenous carboxylates or phosphates in the bidentate μ-1,3-bridged mode. The coordination geometries of Cu(1) and Cu(2) are both distorted square pyramids.     

A 2D Layer Copper(Ⅱ) Coordination Polymer with 3-Nitrophthalic Acid: Synthesis,Crystal Structure and Copper 3-Nitrophthalate Metal-organic Framework-graphene Oxide Nanocomposite

A 2D layer Cu(Ⅱ) coordination polymer [Cu(npth)(H_2O)]n(1) was crystallized from a mixture of 3-nitrophthalic acid and Cu(OAc)_2·H_2O in water under room temperature and structurally characterized by single-crystal X-ray diffraction, FT-IR and TGA. Compound 1 was applied to make a nanocomposite with graphene oxide(GO). A highly dispersible and stable nanocomposite of Cu(npth)-GO was successfully synthesized by a simple ultrasonication method. SEM, TEM, UV-vis, FT-IR and TGA were used to characterize the morphology and structure of the prepared composite. In accordance with the characterization results, we suspected that the binding mechanism of Cu(npth) and GO was assigned to be the cooperative interaction of Cu–O coordination, π-π stacking and hydrogen bonding.     

A Fe(Ⅱ) Coordination Polymer Based on 1,10-Phenanthroline Derivative and Oxalic Acid:Synthesis,Structure,and Properties

A Fe-based coordination polymer,[Fe(C₂O_4)_0.5(4-NCP)]_n·2nH₂O (1,4-HNCP=2-(4-carboxyphenyl)-1H-imidazo(4,5-f)-(1,10)phenanthroline,H₂C₂O₄=oxalic acid),was hydrothermally synthesized and characterized by infrared spectrum,elemental analysis,single-crystal X-ray diffraction,power X-ray diffraction,and UV-vis absorption spectrum.Structural analyses reveal that polymer 1 possesses a (4,4)-connected 2D network.In addition,1 shows photocatalytic activity toward the degradation of rhodamine B (RhB) in the presence of H₂O₂ under visible light illumination.     

Temperature-dependent Syntheses of Two Manganese(Ⅱ) Coordination Compounds Based on an Ether-bridged Tetracarbolylic Acid

0D dinuclear manganese(Ⅱ) coordination compound and 1 D chain manganese(Ⅱ) coordination polymer, namely [Mn_2(μ-L)(phen)4]·4 H_2 O(1) and {[Mn_2(μ5-L)(phen)_2]·H_2O}n(2), have been constructed hydrothermally using H4 L(H4 L = 2,3,3',4'-diphenyl ether tetracarboxylic acid), phen(phen = 1,10-phenanthroline), and manganese chloride at 120 and 160℃, respectively. 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. Single-crystal X-ray diffraction analyses revealed that two compounds crystallize in the triclinic or monoclinic system, space group P1 or P2_1/c. Compound 1 discloses a discrete dimeric structure, which is assembled into a 3 D supramolecular framework through O–H···O hydrogen bond. Compound 2 has a chain structure. Structural differences between compounds 1 and 2 are attributed to the different reaction temperature. Magnetic studies for compound 2 demonstrate an antiferromagnetic coupling between the adjacent Mn(Ⅱ) centers.     

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)]·H2O(1, NIP = 5-nitroisophthalate, 3,3'-bpt = 1H-3,5-bis(3-pyridyl)-1,2,4-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 H2 NIP 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.     

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.     

Four New Cu（Ⅱ） Complexes with Benzotriazole-based Ligands： Syntheses,Crystal Structures and Theoretical Investigations

Four new Cu（Ⅱ） complexes with two benzotriazole-based ligands, [Cu2（L^1）2（NO3）2]· 2H2O （1）, [Cu2（L^1）2]·2ClO4·2H2O （2）, [Cu2（HL^2）2（NO3）4]·2CH3COCH3 （3） and [Cu（HL^2）2（Cl）]·Cl·2CH2Cl2 （4）, where HL^1 = 1,3-bis（benzotriazol-2-yl）-2-propanol and HL^2 = 1,3-bis（benzotriazol-1-yl）-2-propanol, were synthesized and structurally characterized by elemental analyses, IR and single-crystal X-ray diffraction analyses. It is revealed that complexes 1～3 have dinuclear structures, while 4 possesses a one-dimensional （1-D） chain structure, which extends in two orthogonal orientations. In 1～4, the coordination numbers of Cu（Ⅱ） centers range from four to six, which may be attributed to the different geometries and coordination abilities of the ligands and anions. The L^1 ligand in complexes 1 and 2 adopts a tridentate di-chelating coordination mode, whereas ligand HL^2 in complexes 3 and 4 has a bidentate bridging coordination mode. The different coordination modes of these two ligands may be explained by the different charges of nitrogen donor atoms in the benzotriazole ring, which has been investigated by density functional theory （DFT） calculations.     

A Dinuclear Cu(Ⅱ)-based Coordination Framework with Two-fold Interpenetrated 3D pcu Topology Displaying Catalytic Activity

A new Cu(Ⅱ) coordination polymer, [Cu2(mip)2(bmix)]n(bmix = 1,4-bis(2-methylimidazole-1-ylmethyl)benzene, H2 mip = 5-methylisophthalic acid), has been hydrothermally synthesized and characterized by elemental analyses, IR, TGA and single-crystal X-ray diffraction. The title compound belongs to the triclinic system, space group P1 with a = 9.435(5), b = 12.241(6), c = 13.666(6), β = 94.396(8)o, V = 1565.5(13) 3, Z = 2, C34H30Cu2N4O8, Mr = 749.70, Dc = 1.590 g/cm3, μ = 1.419 mm-1 and F(000) = 768. The title metal-organic coordination polymer exhibits the first two-fold interpenetrated pcu topological structure assembled by two types of dinuclear copper(Ⅱ) clusters and a flexible bis(imidazole)-based ligand. In addition, the fluorescence and catalytic performances of the complex for the degradation of Congo red azo dye in Fenton-like process were presented.     

Syntheses,Structures,and Photoluminescent Properties of Two Zn(Ⅱ) Coordination Polymers with Helical Chains Structures

Two novel coordination polymers with helical chains, {[Zn(L)(H2O)]?H2O}n(1) and {[Zn(L)(p-bix)]?3.5H2O}n(2), where H2 L = 5-(4-hydroxypyridinium-1-ylmethyl) isophthalic acid and p-bix = 1,4-bis(imidazol-1-ylmethyl)benzene, have been hydrothermally synthesized, and charac-terized by elemental analysis, powder X-ray diffraction(PXRD), IR, thermal gravimetric analyses(TGA) and also by single-crystal X-ray diffraction. Both complexes 1 and 2 crystallize inmonoclinic, space group P21/c. Compound 1 displays a two-dimensional(2D) structure with two distinct types of helical chains; 2 shows a layered coordination polymer with two types of helical chains and features an interesting 2D→3D interdigitated architecture. Meanwhile, the luminescent properties of 1 and 2 have also been investigated in detail.     

Synthesis,Crystal Structure,Thermal Stability,Luminescence and Magnetic Property of a New Mn~Ⅱ Coordination Polymer

One new coordination polymer, [Mn(Hbtc)(bpy)(H_2O)_2]_n 1, was synthesized by the reaction of manganese(Ⅱ) salt under pH-controlled hydrothermal conditions with unsymmetrical polycarboxylic acid of 1,2,4-benzenetricarboxylic acid(H_3btc) and 2,2?-bipyridine(bpy). The structure of complex 1 was characterized by single-crystal X-ray diffraction, IR spectra, powder X-ray analysis, thermal gravimetric analysis(TGA), UV-Vis spectrometry, photoluminescence and magnetic susceptibility. Complex 1 is a one-dimensional(1D) polymeric single-chain structure. Photoluminescence property is quite similar to the bpy ligand. Magnetic susceptibility measurement indicates that 1 shows a weak ferromagnetic coupling between the Mn~Ⅱ ions.     

Synthesis,Crystal Structure and Fluorescent Properties of a 4-Fold Interpenetrating Zn(Ⅱ) Polymer

A new coordination polymer [Zn(isop)(bps)]n 1(H2isop=benzene-1,3-dicer-boxylic acid,bps=4,4'-dipyridyl sulfide) has been prepared and structurally characterized by X-ray diffraction method.It crystallizes in monoclinic,space group P21/n with a=12.1936(11),b=10.7720(9),c=13.0685(11),V=1709.0(3)3,C18H12N2O4SZn,Mr=417.76,Z=4,Dc=1.624g/cm3,S=1.046,F(000)=848,the final R=0.0305 and wR=0.0858 for 3085 independent reflections with Rint=0.0147.Single-crystal X-ray diffraction analyses reveal that 1 is a 4-fold interpenetrating diamondoid network.The zinc(Ⅱ) atom is coordinated by two nitrogen atoms of two bps and two carboxylate oxygen atoms of isop ligands,resulting in a tetrahedral geometry.     

Synthesis, Crystal Structure and Luminescence Property of a 2D Mn（II） Coordination Polymer Based on Isoniazid

A novel 2D Mn(Ⅱ) coordination polymer [Mn(CH3COO)2(INH)]n(INH=isoniazid) has been synthesized in DMF solution with isoniazid and Mn(CH3COO)2 . The polymer was characterized by single-crystal X-ray diffraction analysis, FTIR and X-ray powder diffraction (XRPD). The crystal belongs to the monoclinic system, space group P2 1 /c with a=9.3251(18), b=16.340(3), c=8.8096(17) , β=94.747(3)°, V=1337.7(4) 3 , Z=4, μ(MoKα)=1.006 mm -1 , F(000)=636, R=0.0754 and wR=0.1375 (I > 2σ(I)). In the complex, each Mn(Ⅱ) atom is coordinated to three CH3COO- groups and two INH ligands. The Mn(Ⅱ) atoms locate in a distorted coordination octahedron and are bridged by CH3COO- ions to form a 1D S shaped chain extending along the c direction. The INH molecules act as bridges to link the Mn(Ⅱ) atoms of adjacent chains and further construct a lamellar polymer. The remaining coordination site is occupied by an O atom of the other CH3COO-. The experimental results show that the title complex has good luminescence property and could be used as potential optical materials.     

A New Mn(Ⅱ) Coordination Polymer Based on 1H-pyrazolo[3,4-b]pyridin-3-amine: Crystal Structure,Magnetic and Electrochemical Properties

A new polymer formulated as [Mn_3(1,3-BDC)_3(L)(H_2O)_3](1) based on linear trinuclear unit Mn_3(COO)_6 has been synthesized under solvothermal conditions with 1,3-benzenedicarboxylic acid(1,3-H_2BDC) and 1H-pyrazolo[3,4-b]pyridin-3-amine(L) as ligands. The polymer was characterized by the single-crystal X-ray diffraction analysis, infrared spectra, elemental analyses, power X-ray diffraction and TG analysis. It crystallizes in orthorhombic system, space group Pna21, with a = 7.9252(3), b = 17.9740(8), c = 22.3027(10) ?, Mr = 845.35, Z = 4, V = 3177.0(2) ?3, F(000) = 1708, D_c = 1.767 g/cm~3, μ(Mo Kα) = 1.257 mm~(-1), the final refinement give R = 0.0388 and w R = 0.0955 for 5595 reflections with I 2σ(I). The polymer 1 can be symbolized as a pcu topology based on the Mn_3(COO)_6 as a secondary building unit. Furthermore, the magnetic properties and electrochemical properties of 1 are also investigated.     

Synthesis and Crystal Structure of a New(6,3)-Connected Ni(Ⅱ) Coordination Polymer

The coordination polymer [Ni(dpa)(bpp)]n(H2dpa = 2,4'-biphenyl-dicarboxylic acid,bpp = 1,3-di(4-pyridyl)propane) was hydrothermally prepared and characterized by single-crystal X-ray diffraction,FTIR spectra,elemental analysis and thermal analysis.The crystal is of triclinic system,space group P1 with a = 12.516(5),b = 12.943(5),c = 15.130(5) ,α = 94.331(5),β = 91.827(5),γ = 108.382(5)°,C54H44N4Ni2O8,Mr = 497.18,V = 2315.3(15) 3,Dc = 1.426 g/cm3,F(000) = 1032,μ = 0.875 cm-1,Z = 2,the final R = 0.0496 and wR = 0.1100 for 5365 reflections with Ⅰ 2σ(Ⅰ).X-ray diffraction analysis reveals that the carboxylate group of 2,4'-diphenic acids acting as bridging ligands adopts two coordination modes:bis-mondentate and bidentate chelating.The compound exhibits a two-dimensional(6,3)-connected architecture.     

One New 3D Pillared-layer Ag(Ⅰ)-Coordination Framework Based on a Unique 1D Ag_2O_2 Ribbon: Synthesis,Crystal Structure and Luminescent Properties

A new 3D Ag(I) coordination polymer {[Ag(AZDB)_(0.5)(bpe)_(0.5)]·H_2O}_n(1) has been papared by azobenzene-3,3?-dicarboxylicate(H_2AZDB), 1,2-bis(4-pyridyl)ethylene(bpe) and silver salts via hydrothermal method. The compound was fully characterized by single-crystal X-ray diffraction, elemental analyses, infrared spectrum(IR), powder X-ray diffraction(PXRD) and thermogravimetric analysis(TGA). The strucrural analysis indicate that compound 1 shows a 3D pillared-layer framework constructed from a unique 1D Ag_2O_2 ribbon and pyridyl/carboxylicate mixed system, which features a 2-nodal(4, 6)-connected fsc net with a(44·610·8)(44·62) topology.Moreover, the photoluminescent properties have also been discussed.