Syntheses, Crystal Structures, and Properties of Two Mixed-ligand Coordination Polymers： [Zn（bdc）（1,3-bimb）]_n and {[Mn_2（ox）_2（1,3,5-tib）_（4/3）]·4H_2O}_n

Two new coordination polymers,[Zn（bdc）（1,3-bimb）]n（1） and {[Mn2（ox）2（1,3,5tib）4/3]·4H2O}n（2）（H2ox = oxalic acid,H2bdc = terephthalic acid,1,3-bimb = 1,3-bis（imidazol-1ylmethyl）benzene,1,3,5-tib = 1,3,5-tri（imidazol-1-yl）benzene）,were synthesized and characterized by elemental analysis,IR,powder X-ray diffraction（PXRD）,and thermogravimetric（TG） analyses.X-ray diffracation analysis reveals that two kinds of zigzag chains [Zn（bdc）]n and [Zn（1,3-bimb）]n in compound 1 are interweaved to form a 3D 4-fold interpenetrated 66-dia framework.In compound 2,Mn（1） and Mn（2） are linked via 1,3,5-tib ligands to form two different nets of [Mn6（1,3,5-tib）6 ]n along the ab plane with inner-or outer-shape N–Mn–N angles,which are connected by 1D infinite [Mn2（ox）2 ]n chains via Mn–O bonds to result in a（3,3,3,4,4）-connected（4·8·10）3（4·82）3（4·83·102）6（82·104·3）3（83）4 topology.Moreover,the photoluminescence of 1 has been investigated.The crystal of 1 crystallizes in orthorhombic,space group Pna2 with a = 13.2267（6）,b = 9.1717（4）,c = 17.4492（8）,V = 2116.79（16）3,Z = 4,C22 H18N4O4 Zn,Mr = 467.77,Dc = 1.468 g/cm3,F（000） = 960 and μ（MoKα） = 1.197 mm-1.The final R = 0.0280 and wR = 0.0618 for 3695 observed reflections with I 2（I） and R = 0.0389 and wR = 0.0653 for all data.The crystal of 2 crystallizes in rhombohedral,space group R-3 with a = 22.080（8）,c = 31.19（2）,V = 13167（11） 3,Z = 18,C24 H25 Mn2 N8 O13,Mr = 743.40,Dc = 1.688 g/cm3,F（000） = 6822 and μ（MoKα） = 0.945 mm-1.The final R = 0.0429 and wR = 0.1035 for 5160 observed reflections with I 2（I） and R = 0.0824 and wR = 0.1244 for all data.     

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 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 Topology Analysis of One Novel Interpenetrated 2D Cobalt Coordination Polymer, {[Co(HTCB)(4,4'-btb)]·H_2O}_n

One novel cobalt coordination polymer, {[Co(HTCB)(4,4'-btb)]·H2O}n(1, H3TCB= 1,3,5-tris(4-carboxyphenyl)benzene, 4,4'-btb = 4,4'-bis(1,2,4-triazol-3-yl)biphenyl), has been synthesized and characterized by elemental analysis, IR, powder X-ray diffraction(PXRD), and thermogravimetric(TG) analyses. X-ray diffraction analysis reveals that complex 1 is a 2D 2-fold interpenetrated {44,62}-sql [Co(HTCB)(4,4'-btb)] sheet based on the 1D [Co(HTCB)]n chains and1 D [Co(4,4'-btb)]n chains. The crystal of 1 crystallizes in triclinic, space group P 1 with a =9.529(12), b = 13.914(16), c = 14.906(17), V = 1903(4) 3, Z = 2, C45H34N6CoO7, Mr = 829.71,Dc = 1.448 g/cm3, F(000) = 858 and μ(MoKα) = 0.514 mm-1. The final R = 0.0655 and wR = 0.1136 for 6603 observed reflections with I 2σ(I) and R = 0.1136 and wR = 0.1747 for all data.     

Crystal Structures and Spectroscopy of Anti-2,4-bis（3-R-phenyl）pentane-2,4-diols （R = Me, SMe）

Two anti-2,4-bis(3-R-phenyl)pentane-2,4-diols (1, R = Me; 2, R = SMe) have been synthesized and were characterized by X-ray diffraction, IR and UV spectra. X-ray diffractions indicate that intra- and intermolecular hydrogen bonding interactions form one-dimensional (1D) ribbons. The adjacent infinite 1D ribbons result in 3D supramolecular structures. The dihedral angles between every two benzene rings in the two diols are 31.61(12) and 31.80(7)°, respectively. UV absorption spectra of the title compounds were recorded in MeOH, C2H5OH, CH3CN, n-BuOH and cyclohexane solvents with different dielectric constants.     

Microwave-assisted Syntheses and Crystal Structures of Benzimidazole Thiazolinone Derivatives

A rapid and efficient microwave-assisted synthesis method for the preparation of 3-(1H-benzo[d]imidazol-2-yl)-2-substituted phenyl thiazolidin-4-one (4a, 4b) was described. The structures of 4a and 4b were determined by elemental analyses, IR, 1H NMR and X-ray diffraction. In the crystals of compounds 4a and 4b, the imidazole ring and two benzene rings are planar. Interestingly, the dihedral angle between two benzene rings is 71.5° in 4a, while it is almost perpendicular in 4b due to the different benzene substituents. Meanwhile, the thiazolidinone ring is planar in 4a while slightly distorted with an r.m.s deviation of 0.1494(2) in 4b. The hydrogen bonding interactions observed link the molecules to form a dimeric unit, which may be effective in the stabilization of the structure.     

Synthesis,Structure and Magnetic Property of a New Three-dimensional Copper(Ⅱ) Coordination Polymer Constructed from 5-Tert-butyl Isophthalic Acid and N-donor Ligand

A new 3D copper(Ⅱ) coordination polymer, {[Cu_2(tbip)_2(1,3,5-tib)]×2H_2O}n(1, H_2 tbip = 5-tert-butyl isophthalic acid, 1,3,5-tib = 1,3,5-tris(1-imidazolyl)benzene), has been synthesized by hydrothermal reaction of Cu(OAc)_2·4H_2O, H_2 tbip and 1,3,5-tib. It has been structurally characterized by element analysis, IR and magnetic measurement. X-ray single-crystal analysis was carried out for 1, which crystallizes in the triclinic system, space group P1 with a = 7.822(3), b = 15.854(6), c = 17.553(6) ?, a = 113.033(4), β = 90.694(4), g = 101.006(4)°, V = 1957.3(12) ?~3, Z = 1, D_c = 1.493 g/cm~3, M_r = 1759.70, F(000) = 908, R = 0.0721 and w R = 0.1978 with I 2s(I). The single-crystal X-ray diffraction studies reveal that compound 1 exhibits 2D [Cu(tbip)] layers which are further pillared by 1,3,5-tib ancillary ligand with terminal tridentate coordination mode to generate the final 3D structure. Magnetic susceptibility data for 1 have been measured in the range of 2~300 K. There are antiferromagnetic interactions between copper ions of the compound.     

Crystal Structure and Property Research on Compounds Co（Ⅱ） and Zn（Ⅱ） with 3-Methylbenzoic Acid

Two compounds with 3-methylbenzoic acid(HL) [Co(L)2(4,4'-bipy)]n 1 and [Zn2(L)4(4,4'-bipy)]n 2(L = 3-methylbenzoic acid) have been hydrothermally synthesized directly and characterized by single-crystal X-ray diffraction analysis,elemental analyses,IR spectra and ultraviolet-visible diffuse reflection integral spectra(UV-Vis DRIS).The two compounds are both one-dimensional infinite chains.The structural difference is that 1 is a double-chain structure and 2 is only a single chain one.At the same time,the carboxylate groups adopt different modes in the two compounds,relatively.Additionally,in order to explore the structural characteristic,two-dimen-sional IR spectra are investigated for 1 and 2.Photo-luminescent property of 2 is also researched in detail.     

Synthesis,Structure, and Luminescent Properties of Two Complexes Based on Flexible Phenylenediacetate Ligand

Two new Zn(Ⅱ) and Cd(Ⅱ) coordination complexes, [Zn(ppda)(idz)]_n(1) and [Cd(mpda)(mbib)]_n(2)(H2 ppda = 1,4-phenylenediacetic acid, H_2 mpda = 1,3-phenylenediacetic acid, idz = imidazole, mbib = 1,3-bis(imidazol-1-ylmethyl)benzene), have been synthesized by using Zn(Ⅱ)/Cd(Ⅱ) salt and phenylenediacetic acid in the presence of different imidazole ligands under hydrothermal conditions, and characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography and thermogravimetric analysis. Complex 1 crystallizes in orthorhombic system, Iba2 space group. The carboxylic acid ligands form a 2 D helical layer with Zn(Ⅱ) ions, and such layers are expanded into a 3 D network structure by the force of C–H×××π. Complex 2 crystallizes in monoclinic system, P2_1/n space group. Complex 2 shows a 3 D framework with two Cd(Ⅱ) ions as nodes of a dual-core unit, which can be considered to be 6-connected net and regarded as a rare(4~4,5~(10),7) topology network with self-interlacing. The structural diversities indicate that rigid and flexible imidazole ligands play dominating roles in modulating the formation of structures of these crystalline materials. Moreover, the luminescent properties of two complexes are investigated in solid state.     

Syntheses,Structures, and Properties of Three Coordination Polymers: [Cd_2(bpp)_(1.5)(Hbpp)(phen)_2]_n, [Mn_3(Htptc)_2(phen)_2(H_2O)_2]_n,and {[Cu(btc)_(0.5)(1,4-bib)]·2H_2O}_n

Hydrothermal reactions of three aromatic polycarboxylic acids and the transitional metal cations in the presence of phen and 1,4-bib afford three new coordination polymers: [Cd2(bpp)1.5(Hbpp)(phen)2]n(1), [Mn3(Htptc)2(phen)2(H2O)2]n(2), and {[Cu(btc)0.5(1,4- bib)]·2H2O}n(3)(H2bpp = 2,6-bis(4'-carboxyphenyl)-4-phenylpyridine, H4tptc = terphenyl-2,5,2',5'-tetracarboxylic acid, H4btc = biphenyl-2,2',4,4'-tetracarboxylic acid, phen = 1,10-phenanthroline, and 1,4-bib = 1,4-bis(1H-imidazol-1-yl)benzene). Their structures have been determined by singlecrystal X-ray diffraction analyses, elemental analyses, IR spectra, and powder X-ray diffraction(PXRD) analyses. In compound 1, the CdII cations are linked by bpp2- to form one ladder structure, based on which a 3D network is constructed with the help of non-covalent interactions. The topology of 2 is a 3D(3,4,5)-connected framework with the Point Schl?fli symbol of(42.6)32(4.62.8)(45.64.8)2. Compound 3 shows an unprecedented 3D(4,4)-connected framework with the Point Schl?fli symbol of(64.82)2(65.8). Moreover, the luminescent property of 1 has been investigated.     

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.     

A 3D Ba(Ⅱ) Inorganic-organic Hybrid Framework Based on 1,3,5-Benzenetricarboxylic Acid Ligand: Synthesis and Characterization

A three-dimensional(3D) barium complex with 1,3,5-benzenetricarboxylic acid(H3BTC), {[Ba1.5(BTC)(H2O)]·(H2O)}n(1), was synthesized in DMF/EtOH/H2 O mixed solution under solvothermal conditions, and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, thermogravimetric analyses, and photoluminescence measurement. In complex 1, the 2D I2O0 type inorganic layer is constructed by {Ba1O10} and {Ba2O9} polyhedra. Moreover, the solid-state fluorescence measurement reveals a fluorescence emission band at 465 nm under 344 nm excitation, assigned to a charge-transfer transition.     

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.     

Two Metal Ion-controlled Zn(Ⅱ)/Cd(Ⅱ) Coordination Polymers Based on 1,3,5-Benzenetricarboxylic Acid

Two new coordination polymers {[Zn(Hbtc)(bpyb)]·H_2O}n(1) and {[Cd(Hbtc)-(bpyb)_(1.5)]·0.5 bpyb}_n(2)(H_3btc = 1,3,5-benzenetricarboxylic acid, bpyb = 1,4-bis(4-pyridyl)benzene) have been synthesized under hydrothermal conditions. The two compounds were characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. Compound 1 displays a 2-fold interpenetrating 3D supramolecular architecture through O–H···N/O hydrogen bonds and π-π stacking interactions. Compound 2 exhibits a 2D→3D polycatenated structure, which is further stabilized by O–H···N hydrogen bonds. The results indicate that the metal ion has significant effects on the formation and structure of the resulted coordination polymers. Furthermore, thermal stability and photoluminescent properties of 1 and 2 are also discussed in detail.     

Syntheses and Crystal Structures of a Cadmium(Ⅱ) and a Zinc(Ⅱ) Complexes with the Flexible Ligand 1-Acetic Acid-2, 2'-biimidazole

Reactions of NaAcebiim(NaAcebiim = 1-acetic acid-2, 2′-biimidazole monosodium salt) and cadmium or zinc nitrate produce two supramolecular architectures, namely, 1D [Cd(Acebiim)(NO3)(H2O)]n(1) and 0D [Zn(Acebiim)2(H2O)2]·2H2O(2) in acidic aqueous solutions. Single-crystal X-ray diffraction analysis reveals that complex 1 crystallizes in the triclinic system, space group P1, and 2 is of monoclinic system, space group P21/n. In 1, two nitrate groups link two Cd(Ⅱ) ions forming [Cd2(NO3)2(H2O)2] as secondary building units that are interconnected by the Acebiim- ligand into an infinite ladder. In 2, the hydrogen-bonded synthon R22(16) between the N–H moieties and carboxylic acid link [Zn(Acebiim)2(H2O)2], generating a 1D-extended ribbon. Moreover, hydrogen bonds and π-π interactions further stabilize the 3D supramolecular architecture.     

Hydrothermal Synthesis and Structural Characterization of Two Zinc Coordination Polymers of 1,2‐Di(4‐pyridyl)ethylene and Benzenedicarboxylate

Hydrothermal reactions of Zn(NO3)2•6H2O with 1,2-di(4-pyridyl)ethylene (dpe) and 1,4-benzenedicarboxylate (1,4-BDC) or 1,3-benzenedicarboxylate (1,3-BDC) in water gave rise to two new metal-organic coordination polymers, [Zn(1,4-BDC)(dpe)]n (1) and [Zn4O(1,3-BDC)3(dpe)]n (2). Both compounds were characterized by elemental analysis and IR spectroscopy, and their structures were determined by single crystal X-ray diffraction. 1 displays a rare 5-fold interpenetrating 66-diamondoid framework while 2 possesses an interlocked 3D network formed by inclined interpenetration of 2D (4,4) networks that are constructed by μ4-oxo tetrazinc Zn4O cores and the bridging dpe and 1,3-BDC ligands. Thermal and photoluminescent properties of 1 and 2 were also investigated.     

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.     

Application of 4,4＇-（2-Carboxypropane-1,3-diyl）dibenzoic Acid in Coordination Metal Complexes： Synthesis,Characterization, and Theoretical Studies①

[Pb(HL)(phen)]n(1) and [Cd3L2(phen)]n(2), where phen = 1,10-phenanthroline and L = 4,4'-(2-carboxylatopropane-1,3-diyl)dibenzoate, were hydrothermally prepared and fully characterized by X-ray single-crystal diffraction, infrared spectroscopy and thermogravimetric analyses. The decomposition temperature of 1 and 2 was measured to be ca. 304 and 416 ℃, respectively. The charge transfer transition based absorption of 1 and 2 was also verified by the powder scattering spectra and theoretical analyses.     

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.     

Synthesis,Structure and Properties of Three-dimensional Gd(Ⅲ),Eu(Ⅲ) Coordination Polymers via in situ Decarboxylation

Two three-dimensional lanthanide(Ⅲ) coordination polymers with the formula [Ln(PYDC)(NA)(H2O)]n [Ln=Gd(1), Eu(2), H2PYDC=pyridine-2,5-bicarboxylic acid, HNA=nicotinic acid] have been hydrothermally synthe- sized and characterized by elemental analysis, IR, and single crystal X-ray diffraction. The NA came from in situ decarboxylation of the part of PYDC. X-ray single crystal structural analyses reveal that complexes 1 and 2 are iso- morphous, they possess the 43·63 topology assembled by Gd3+/Eu3+ and two di...