Synthesis,Crystal Structure and Antifungal Activity of a New Ho(Ⅲ) Complex Based on 4,4?-Dicarboxybiphenyl Sulfone

A new lanthanide coordination polymer, [Ho(sba)(H_2O)_2(DMF)_2]×H_2O×DMF×Cl(1) based on the versatile ligand H2sba(H2sba = 4,4?-dicarboxybiphenyl sulfone), was prepared and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and thermogravimetric analysis. Single-crystal X-ray diffraction indicates that complex 1 belongs to the triclinic system, space group P1 with a = 10.6942(6), b = 11.8452(7), c = 13.1814(8) ?, α = 94.854(2), b = 96.649(2), γ = 91.663(2)o, V = 1651.30(17) ?3, Z = 2, Dc = 1.565 g·cm~(-3), μ = 2.597 mm~(-1), Mr = 777.98, F(000) = 780, the final R = 0.0446 and w R = 0.1116 with I 2s(I). In the title complex, the Ho(III) ions exhibit 1D ∞-like double chains. The DMF molecules not only make the structure more stable, but also act as hydrogen bond acceptors making the 1D double chains into a three-dimensional(3D) supramolecular framework. In addition, the antifungal effects of the ligand, metal salt and Ho(III) complex have also been studied by the disc diffusion method against Colletotrichum gloeosporioides Penz. It was found that the antifungal activity of complex 1 was better than the corresponding ligand and the metal salt. Complex 1 has potential applications in the antifungal activity.     

Synthesis,Crystal Structure,Fluorescent Property and DFT Calculations of a New Zn(Ⅱ) Complex Based on 3-(2-Pyridyl)-5-(4-pyridyl)-1H-1,2,4-triazole

A new coordination compound Zn(2,4?-bpt)2(H_2O)(1) based on the versatile ligand 2,4?-Hbpt(2,4?-Hbpt = 3-(2-pyridyl)-5-(4-pyridyl)-1H-1,2,4-triazole) was prepared by hydrothermal reactions. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, X-ray powder diffraction, IR spectrum analysis and thermogravimetric analysis. Single-crystal X-ray diffraction analysis indicates that the complex belongs to monoclinic system, space group C2/c with a = 23.877(3), b = 0.7483(9), c = 1.2492(2) ?, b = 92.681(2)°, V = 2230.6(4) ?3, Z = 4, Dc = 1.572 g/cm~3, m = 1.143 mm~(-1), Mr = 527.85 and F(000) = 1080. The final R = 0.0581 and w R = 0.0898 with I 2s(I). 1 is a 0D motif which is connected by hydrogen bonds to form a corrugated 1D pattern. In addition, 1 shows strong photoluminescent emissions in the solid state at room temperature which can be used as potential optical materials. Theoretical calculations based on density functional theory(DFT) were employed in order to explicate the stability and chemical reactivity of 2,4?-Hbpt with different conformations. The results indicated that conformation I is more stable and prior to coordination in the reactions.     

A New 3d-4f Heterobimetallic Complex Based on 4,4?-Dicarboxybiphenyl Sulfone: Synthesis,Crystal Structure and Antifungal Activity

A new 3 d-4 f heterobimetallic complex [PrCu(sba)_2(Hsba)(H_2 O)_3]·H_2 O(1) based on a versatile ligand H_2 sba(H_2 sba = 4,4?-dicarboxybiphenyl sulfone) was prepared and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and thermogravimetric analysis. Single-crystal X-ray diffraction indicates that complex 1 belongs to the monoclinic system, space group P2_1/n with a = 12.4642(11), b = 16.0586(16), c = 21.9678(19) ?, β = 92.888(1)o, V = 4391.4(7) ?~3, Z = 4, D_c = 1.800 g·cm~(-3), μ = 1.812 mm-1, M_r = 1190.31, F(000) = 2388, the final R = 0.0663 and wR = 0.1539 for 7737 observed reflections with I 2s(I). Complex 1 exhibits 2D network skeletons which are linked by hydrogen-bonding interactions to give a 3D supramolecular architecture. In addition, the antifungal effects of H_2 sba, metal salts and the title complex have also been studied by disc diffusion method against Colletotrichum gloeosporioides Penz. Complex 1 has better antifungal activity than H_2 sba and the corresponding metal salts. Complex 1 has potential applications in the antifungal activity.     

Synthesis and Crystal Structure of a Novel Ca(Ⅱ) Coordination Polymer Containing Dipyridine Dicarboxylic Ligand

The novel alkaline metal complex Ca(BPDCH)2(1, BPDCH2 = 2,2'-bipyridine-5,5'-dicarboxylic acid) has been synthesized by the hydrothermal reaction of Ca(NO3)2·4H2O with 2,2'-bipyridine-5,5'-dicarboxylic acid. The molecular and crystal structures of complex 1 have firstly been characterized by FTIR, elemental analysis, and X-ray single-crystal diffraction. The 3D MOF structure of complex 1 was interpreted by the versatile binding modes-the intermolecular hydrogen bonds and π-π stacking interactions of 2,2'-bipyridine-5,5'-dicarboxylic acid ligand. The analysis results show complex 1 belongs to a coordination polymer with 3D MOF structure. The results of thermogravimetric analysis and solubility demonstrate complex 1 is a thermostable compound and does not dissolve in water and traditional organic solvents.     

Syntheses,Structure and Properties of a Strontium(Ⅱ) Complex with 5-Sulfoisophthalic Acid Monosodium

A new Sr(Ⅱ) complex, [Sr(Hsip)(H2O)](1, NaH2sip = 5-sulfoisophthalic acid monosodium), has been synthesized by solvothermal reaction of Sr CO3 and NaH2sip at 120 ℃, and characterized by single-crystal X-ray diffraction studies, elemental analysis and FT-IR. Singlecrystal X-ray diffraction reveals that compound 1 has a 3D architecture, and there is only one crystallographically independent Sr(Ⅱ) ion in 1. The coordination geometry of Sr(Ⅱ) is a distorted tetragonal anti-prism. The whole Hsip2- ligand performs a μ6-coordination model. In the solid state, complex 1 shows luminescence with the maximum emission intensity at 417 nm upon excitation at 320 nm. Thermal stability of complex 1 was also investigated.     

Two Carboxylato-bridged Binuclear Cobalt(Ⅱ) Complexes Pillared Coligands: Synthesis,Structures and Magnetic Properties

By adopting mixed-ligand strategy, two Co(Ⅱ) coordination polymers, [Co(phda)(itmb)(H_2O)_2]_n(1) and [Co(phda)(Hpytz)]_n(2)(H_2phda = 1,2-phenylenediacetate, itmb = 1-(imidazo-1-ly)-4-(1,2,4-triazol-1-yl methyl) benzene and Hpytz = 3,5-di(4-pyridyl)-1,2,4-triazolate), were hydrothermally synthesized and then characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis(TGA), powder X-ray diffraction(PXRD) and single-crystal X-ray diffraction. The single-crystal X-ray diffraction reveals that two complexes feature carboxylato-bridged binuclear subunits extended further by the nitrogen-rich coligands to form different structures. Complex 1 containing phda-bridged binuclear cobalt is developed by itmb coligand to 1D double-stranded chain, whereas complex 2 exhibits 2D open bilayers, which result from the ribbon-like carboxylate chains pillared Hpytz coligands. In addition, the magnetic susceptibilities of both compounds were measured over the temperature range of 3～300 K, and the data were analyzed well using Mag Saki software. The best fitting parameters were κ = 0.98, λ =-100 cm~(-1), ? = 588 cm~(-1) and J = 0.6 cm~(-1) for complex 1 and κ = 0.86, λ =-110 cm~(-1), ? = 756.8 cm~(-1) and J =-1.25 cm~(-1) for complex 2. The results indicate the existence of weaker ferromagnetic interaction for complex 1 and antiferromagnetic interaction for complex 2 between the metal centers in the dinuclear metal units.     

Synthesis,Crystal Structure and Luminescent Property of a Ag(Ⅰ) Coordination Polymer with a 3D Sandwich-like Framework

A new coordination polymer,{[Ag_2(bpp)_2(H_2O)_2]·bpdc·3H_2O}_n,derived from the ligand biphenyl-4,4'-dicarboxylic acid(H_2bpdc),has been obtained through a hydrothermal technique(bpp = l,3-bis(4-pyridyl)propane).Its single-crystal structure has been characterized by single-crystal X-ray diffraction,powder XRD,FT-IR,TGA and elemental analysis techniques.The single-crystal X-ray diffraction reveals that complex 1 consists of 1D infinite[Ag(bpp)(H_2O)]_n~(n+)cationic chains,2D anionic layer constructed by bpdc anions and free water which provide charge compensation in the crystal structure.The 1D infinite[Ag(bpp)(H_2O)]_n~(n+) cationic chains and 2D anionic layer are further stacked in-ABAB- fashion through intermolecular H-bonding to form a 3D sandwich-like framework.In addition,the luminescent property of complex 1 in the solid state at room temperature was investigated.     

Hydrothermal Synthesis,Crystal Structure and Properties of a Novel 3D Metal-organic Coordination Polymer with Helical Chains Based on 5-(Imidazol-1-ylmethyl)isophthalic Acid

A novel 3D metal-organic coordination polymer with helical chains based on a flexible 5-(imidazol-1-ylmethyl)isophthalic acid(H_2L) as a main ligand and 1,2-bis(4-pyridyl)ethane(bpa) as a N-containing ancillary ligand,[Cd L(bpa)_(0.5)]_n(1),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.It crystallizes in monoclinic,space group P2_1/c with a = 10.984(2),b = 10.1829(12),c = 17.782(3) ?,β = 123.156(11)o,V = 1665.1(5) ?~3,Z = 4,Mr = 448.72,Dc = 1.790 g/cm~3,Rint = 0.0871,F(000) = 892,the final R = 0.0687 and w R = 0.1294 for 2920 observed reflections(I 2σ(I)).In complex 1,the L~(2-) anions connect Cd(Ⅱ) ions to form two-dimensional metal-organic layers(Cd_2L_2)n,in which the 1D helical chains(Cd-L)_n are alternately arranged in a right-and left-handed sequence.These layers are further linked to build a 3D network by the bpa ligand.In addtion,photoluminescent properties for 1 are also investigated.     

Syntheses,Structures,Fluorescence and Heterogeneous Catalysis of Coordination Polymers with 4-Benzoimidazol-1-yl-methyl Benzoic Acid and 2,2′-Dipyridine

Two coordination polymers called [Ni(L)_2]_n(1) and [Ni(2,2?-bpy)_22(H_2O)]n (2)(HL = 4-benzoimidazol-1-yl-methyl benzoic acid, 2,2?-bpy = 2,2?-dipyridine) were synthesized by solvothermal reaction simultaneously and characterized by elemental analyses, thermogravimetric analysis, X-ray powder diffraction, IR spectroscopy and single-crystal X-ray diffraction analysis. Complex 1 crystallizes in monoclinic system, space group P2_1/c with a = 14.673(3), b = 10.773(2), c = 16.566(3) ?, V = 2559.2(8) ?~3, Z = 4 and F(000) = 1160. 2 also crystallizes in monoclinic system, space group C2/c with a = 15.404(3), b = 12.652(3), c = 6.5362(13) ?, V = 1246.2(5) ?~3, Z = 4 and F(000) = 712. The bridging L ligand connects the Ni~Ⅱ cations into a 2D network in complex 1, while 2 shows a 1D structure formed through the two O atoms of SO_4~(2-) ions connecting the molecule. The catalytic properties indicate that complex 1 shows good catalytic activities for the cyanosilylation of 4-chlorobenzaldehyde. In addition, fluorescence property of complex 1 which quenches the excitation intensity in solid state was investigated at room temperature.     

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.     

三维配合物[Zn_2(OH)(pyim)(BIPA)]_n的水热合成、晶体结构和荧光性质研究(英文)

Hydrothermal reaction between 5-bromoisophthalic acid (H2BIPA) and Zn(NO3)2·6H2O at the presence of the second ligand of 2-(2-pyridyl)imidazole (Hpyim) yields a new 3D metal-organic coordination polymer [Zn2(OH)(pyim)(BIPA)]n (1),which has been characterized by single-crystal X-ray diffraction,elemental analysis,IR spectrum and thermal analysis. Complex 1 presents an α-Po net with 41263 topology constructed from tetranuclear clusters and displays strong luminescent emission 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 New Two-dimensional Zinc Coordination Polymer Constructed by 1,3-Bis(4-pyridyl)-propane and Terephthalate: Synthesis and Crystal Structure

A new zinc coordination polymer, [Zn2(bpp)(tpa)2H2O] 1 (bpp=1,3-bis(4-pyridyl)-propane and tpa=terephthalate) has been hydrothermally synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. X-ray crystal structure analysis reveals that complex 1 crystallizes in monoclinic, space group P2/c with a=18.348(2), b=10.9080(14), c=13.7924(18), β=98.156(2)°, V=2732.5(6)3 , Z=4, C29H24N2O9Zn2 , Mr=675.24, Z=4, F(000)=1376, Dc=1.641 mg/m3 , μ=1.815 mm-1 , the final R=0.0443 and wR=0.0769 for 2715 observed reflections (I>2σ(I)). The title complex exhibits a two-dimensional (4, 4) sheet structure which is further stacked through face-to-face π-π interactions between the monodentately coordinated pyridine ring of bpp ligand and the phenyl ring of terephthalate ligand to form a 3-dimensional supramolecular structure. Thermogravimetric analyses show that the host framework of the complex is thermally stable up to ca. 400 ℃.     

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.     

Three New Zn(Ⅱ)/Cd(Ⅱ) Coordination Polymers Constructed with 2-Mercaptonicotinic Acid and 1,2-Di(4-pyridyl)ethylene: Syntheses and Structure Analysis

Three new Zn(Ⅱ)/Cd(Ⅱ) coordination polymers based on 2-mercaptonicotinic acid (H2mna) with 1,2-di(4-pyridyl)ethylene (dpe) introduced as a bridging ligand have been synthesized via hydrothermal method and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. As reported in this paper, [Zn2(dpe)0.5(mna)2] (1) can be classified as a two-dimensional layer structure in which the 1D chain composed of Zn(Ⅱ) and mna ligands is bridged by dpe ligands, while the complex named [Zn4(dpe)4(mna)4] (2) is a tetra-nuclear cluster compound. These two compounds are further extended to three-dimensional structures by hydrogen bonds along with C-H…π and π…π interactions. Compound 3 with general formular [Cd2(dpe)0.5(mna)2]·H2O belongs to a three-dimensional porous structure in which the 2D metal layers formed by the coordination of Cd(Ⅱ) and mna ligands are connected with the bridging of dpe ligands.     

Crystal Structure and Properties of a Copper(Ⅱ) Complex Containing p-Toluenesulfonate and Imidazole Ligands

A novel supramolecular mixed ligand complex of formula [Cu(PTS)2(Him)2(H2O)2] (C20H26CuN4O8S2,PTS=p-toluenesulfonate,Him=imidazole) has been synthesized in aqueous solution and characterized by elemental analysis,IR and single-crystal X-ray diffraction.The compound crystallizes in the monoclinic system,space group P21/n,Z=2,a=5.650(2),b=14.671(3),c=14.638(3),β=100.10(3)°,V=1194.60(4)3,Dc=1.607 g/cm3,μ(MoKα)=1.143 mm-1,F(000)=598,R=0.0615 and wR=0.1503 for 1752 observed reflections with I 2σ(I).The copper(II) ion in the complex adopts a slightly distorted octahedral coordination geometry and is six-coordinated with N2O4 donor set consisting of two nitrogen atoms and four oxygen atoms provided by the ligands of two imidazole molecules,two water molecules and two p-toluenesulfonate ions.The sulfonate group of the PTS ligand remains weak-coordinated and forms a number of hydrogen bonds with water molecules and imidazole ligands.X-ray structural analysis reveals that the coordination molecules are connected to form a 3-D supramolecular framework by electrostatic interaction,weak van der Waals forces,hydrogen bonding and π-π interaction.The thermal behaviour of the title complex was investigated by using DSC and TG-DTG techniques.     

A 3D Nickel(Ⅱ) Complex Constructed by Bis(2-dimethylaminoethyl) Ether: Solvothermal Synthesis,Crystal Structure and Catalytic Properties

Treatment of bis(2-dimethylaminoethyl) ether(BDMAE) with nickel acetate afforded a novel 3D nickel(Ⅱ) complex [Ni(BDMAE)(H_2O)_3·(CH_3COO)_2·(H_2O)_2] under solvothermal conditions. Its crystal structure was characterized by elemental analysis, IR spectrum, PXRD and single-crystal X-ray diffraction analysis. The complex belongs to the orthorhombic system, space group C2221 with a=8.823(2), b=13.932(3), c=17.563(4) ?, V=2158.9(8) ?~3, Z=4, C_(12)H_(36)N_2NiO_(10), Mr=427.14, Dc=1.314 g/cm~3, F(000)=920 and μ=0.944 mm~(-1). Single-crystal X-ray diffraction reveals that the mononuclear nickel(Ⅱ) ion is six-coordinated to one oxygen, two nitrogen atoms of the BDMAE ligand and three oxygen atoms of coordinated water molecules. The complex exhibits a 3D supramolecular structure through a variety of intermolecular and intramolecular hydrogen bonding interactions. In addition, the complex has been investigated for catalytic properties towards the Henry reaction of nitromethane with p-nitrobenzaldehyde, and the results indicated that the 1-p-nitrophenyl-2-nitroethanol product was obtained in excellent yield under optimum conditions with the complex as the catalyst.     

Synthesis and Crystal Structure of N-Benzyl-N＇-（2-pyridyl）urea and Its Mononuclear Cu（Ⅱ） Complex

A new ligand of N-benzyl-N＇-（2-pyridyl）urea L and its self-assembly product with CuCl2, [Cu（Ⅱ）LCl2]∞ 1, have been synthesized and structurally characterized by IR, 1H NMR and single-crystal X-ray diffraction analysis. In the structure of L, the urea groups adopt Z,E conformation to form dimers through intermolecular hydrogen bonds; while in complex 1, it assumes Z,Z conformation to fit for the coordination sphere of the Cu（Ⅱ） ions. The coordinated units are connected through intermolecular N-H...Cl hydrogen bonds to form an extended 2D framework. Finally, a 3D structure is obtained via π-π stacking interactions between pyridyl rings     

Catalytic Kinetic on the Thermal Decomposition of Ammonium Perchlorate with a New Energetic Complex Based on 3,5-Bis(3-pyridyl)-1H-1,2,4-triazole

A new energetic complex,[Co(3,3?-Hbpt)(Htm)]·H_2O(1,3,3?-Hbpt = 3,5-bis(3-pyridyl)-1H-1,2,4-triazole and H_3tm = trimesic acid),has been synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction,elementary analysis,IR spectroscopy,thermogravimetric analysis and X-ray powder diffraction. Single-crystal X-ray diffraction indicates that the complex belongs to triclinic system,space group P 1 with a = 10.0911(1),b = 10.2573(1),c = 10.6393(1) ?,α = 103.793(2),β = 101.041(2),γ = 107.918(3)o,V = 974.9(2) ?~3,Z = 2,D_c = 1.732 g·cm-3,μ = 0.941 mm~(-1),M_r = 508.31,F(000) = 518,the final R = 0.0523 and wR = 0.0935 with I 2σ(I). In the title complex,Co(Ⅱ) ions are connected by Htm2-anions generating 1D ladder-like chains which are linked by 3,3?-Hbpt to form 1D cages. In addition,the thermal decomposition of ammonium perchlorate(AP) with complex 1 was explored by differential scanning calorimetry(DSC). AP is completely decomposed in a shorter time in the presence of complex 1,and the decomposition heat of the mixture is 2.531 kJ·g~(-1),significantly higher than that of pure AP. By Kissinger's method,the ratio of Ea/ln(A) is 11.05 for the mixture,which indicates that complex 1 shows good catalytic activity toward the AP decomposition.     

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.