Flexible Bis(benzimidazole)-based Ligands Directed the Structure Characteristics of Coordination Polymers Based on Diphenic Acid Co-ligands:Syntheses, Structures and Properties

Two new coordination polymers [Cu_2(bbim)(dpa)_2(C_2H_5OH)_2](1), [Co(dpa)_2(bbbm)](2)(H_2dpa = diphenic acid, bbim = 1,1?-(1,6-hexanediyl)bis-1H-benzimidazole, bbbm = 1,1?-(1,4-butanediyl)bis-1 H-benzimidazole) constructed from bis(benzimidazole)-based ligands with different lengths and diphenic acid co-ligand have been synthesized under solvothermal conditions.Complex 1 possesses Cu-dpa helical chains. The adjacent chains are connected by the bbim ligands into two-dimensional(2D) 3-connected(63) topology. Differently, the layer structure of 2 was consisted by one-dimensional chains containing alternated 8-and 18-membered rings. Furthermore,the thermal stability and fluorescence property for all crystalline materials have been investigated.

Construction of Two Coordination Polymers Based on Two New 5-Substitued Tetrazole-based Ligands: Structures and Luminescent Properties

Two new coordination polymers(CPs) based on two new tetrazole-based ligands, namely, [Cu(TPP)]n(HTTP = 4-(3-(2 H-tetrazol-5-yl)phenyl)pyridine, 1) and {[Cd_2(TBCA)_2(H_2O)_2]·-H_2O}n(H_2TBCA = 3?-(2 H-tetrazol-5-yl)biphenyl-4-carboxylic acid, 2), were synthesized via solvothermal reactions. Single-crystal X-ray diffraction analysis reveals that compound 1 exhibits a(3,6)-connected rtl network topology based on binuclear secondary building units(SBUs). Compound 2 presents a 2D framework composed of 1D SUBs formed by both carboxyl and tetrazole groups. The 2D network is linked into a 3D framework via various hydrogen bonds. They represent two examples of CPs construct from rigid 5-substitued tetrazole-based ligands with relatively longer spacer. The thermal stabilities and luminescent properties of compounds 1 and 2 were also explored.

Syntheses, Crystal Structures and Fluorescence Properties of Four Coordination Polymers Based on Enantiomeric 2-(4-Carboxyphenyl)-4,5-dihydrothiazole-4-carboxylic Acid Ligands

A pair of enatiomerically pure ligands,(R-)/(S-)2-(4-carboxyphenyl)-4,5-dihydrothiazole-4-carboxylic acid(H2L^R & H2L^S), have been synthesized by the reactions of 4-cyanobenzoic acid with L-and D-cysteine, respectively. Four coordination polymers have been prepared from the ligands and structurally determined by single-crystal X-ray diffraction analysis. Complexes 1 R and 1 S([NiL(Py)(H2 O)]×H2 O, for 1 R, L =(L^R)^(2-);for 1 S, L =(L^S)^(2-)) exhibit chiral helical one-dimensional chains, and complexes 2 R and 2 S({[ZnL2(H2 O)3]×CH3 CN}n, for 2 R L =(L^R)^(2-), for 2 S L =(LS)^(2-)) are two-dimensional sheets. Luminescent and chir-optical properties have been investigated and compared with the free ligands. The complexes have blue-shift in luminescence spectrum compared with the free ligands.

Syntheses and Crystal Structures of Three Cadmium（II） Coordination Complexes Based on Flexible 1,2-Bis（imidazol-1~ˊ-yl）ethane

Three Cd（II） coordination complexes,{[Cd（bime）3]（NO3）2·（H2O）3}n（1）,[Cd（bime）Br2]n（2） and [（H2bime）（CdBr4）（H2O）]n（3）（bime = 1,2-bis（imidazol-1-yl）ethane）,have been prepared and characterized.Single-crystal X-ray diffraction analysis reveals that 1~3 crystallize in the trigonal space group P-3,monoclinic space group C2/c and triclinic space group P1,respectively.In 1,bime bridges six-coordinated Cd（II） to generate a two-fold interpenetrating 3D coordination polymer,in which NO3- is not involved in coordination,but serves as a void filler to balance the charge of the 3D framework.The six NO3- and six uncoordinated water molecules form an unprecedented 24-membered macrocycle through hydrogen bonding interaction.In 2,bime in an anti-conformation links the CdBr2 units into a zigzag chain.In 3,bime does not take part in coordination,but is protonated to act as a counter cation of [CdBr4 ]2-.The hydrogen bonds between H2bime and [CdBr4]2- result in the formation of a supramolecular chain.

Two Metal-organic Coordination Polymers with Rigid Bis(triazole) Ligand： Assembly, Structures, and Fluorescence Properties

Two new coordination polymers containing rigid bis（triazole）, namely, [Ni（btb）_（0.5）（nph）（H_2O）]_n（1） and [Zn（btb）（SO_4）]_n（2）（btb = 4,4a-bis（1,2,4-triazolyl-1-yl）-biphenyl, H_2nph = 3-nitrophthalic acid） have been synthesized and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. Complex 1 shows a 3D trinodal（3,4,4）-connected sqc69 topology. Complex 2 presents a 2D uninodal 4-connected sql network, which is further packed into a 3D supramolecular framework by C-H···O hydrogen bonds. Thermal stabilities and fluorescence properties of two complexes have been discussed in detail.

Synthesis, crystal structures and fluorescence properties of four mixed-ligands Zn(Ⅱ) and Cd(Ⅱ) coordination compounds

Four new coordination compounds, [Zn(dba)(bpy)]n (1), {[Zn(dba)(phen)]·2H2O}n (2), [Cd(dba)(bpy)(H2O)2] (3) and [Cd2(dba)2(phen)2]n (4) (H2dba = 2,5-dihydroxy-p-benzenediacetic acid, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline) have been prepared via solvothermal method and characterized by sin-gle-crystal X-ray diffraction, infrared spectroscopy, elemental analysis and powder X-ray diffraction. 1 and 2 possess 1D infinite chain structures. Complex 3 exhibits a mononuclear structure. Complex 4 owns binuclear symmetry units, which were bridged via the dba ligands forming a 2D framework. The fluorescence properties of 1―4 have been studied.

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）A,α=93.378（3）,β= 95.471（3）,γ=101.101（3）°,V=1002.6（3）A^3,Mr=834.67,Dc=1.382 g/cm^3,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 I〉2σ（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.

Coordination Polymers with Bipyridyl Diene and Triene Ligands:Synthesis,Structures and Luminescent Properties

Solvothermal reactions of cadmium salts with bipyridyl diene and triene ligands[1,3-bis((E)-2-(pyridin-4-yl)vinyl)benzene-(1,3-bpeb) and 1,6-bis(4-pyridyl)-1,3,5-hexatriene(bphte)] and one bipyridyl triene ligand[1,6-bis(4-pyridyl)-1,3,5-hexatriene-(bphte)] in the presence of auxiliary carboxylic acids including 2,6-dichlorobenzoic acid(2,6-HDCBA) and 2-naphthal-enecarboxylic acid(2-HNCA) gave rise to four coordination polymers[Cd(bphte)(2,6-DCBA)2]n(1), {[Cd(bphte)(2-NCA)2]·5.8H2O}n(2),[Cd2(1,3-bpeb)2(2,6-DCBA)4]n(3) and {[Cd4(1,3-bpeb)4(2-NCA)7(HCOO)]·2-HNCA·H2O}n(4), respectively. Compounds 1-4 were structurally characterized by elemental analysis, IR, 1H NMR, powder X-ray diffraction, thermogravimetric analysis and single-crystal X-ray diffraction. They possess one-dimensional linear(1, 2) and zigzag(3, 4) chain structures. Their luminescent properties were explored while the representative sample 4 exhibited good luminescent performance in sensing Fe(III) in water.

Syntheses and Characterizations of Novel One-dimensional Coordination Polymers Self-assembled from Co(NCS)_2 and Flexible Diester-bridged Pyridine-based Ligands

The self-assembly reactions of Co(NCS) 2 with diester-bridged pyridine-based ligands pyCO 2-(CH 2) m-O 2Cpy (py=4-pyridyl; m=2, 3, 4) have been studied. Interestingly, while Co^(NCS) 2 reacted with pyCO 2-(CH 2) 2-O 2Cpy (La) in MeOH/H 2O or THF/MeCN to yield two coordination polymers [Co^(NCS) 2(La) 2] n(1) and [Co(NCS) 2(La) 2·2THF] n(2), reactions of Co(NCS) 2 with pyCO 2-(CH 2) 3-O 2Cpy (Lb) in MeOH/MeCN and Co(NCS) 2 with pyCO 2-(CH 2) 4-O 2Cpy (Lc) in EtOH/H 2O afforded [Co(NCS) 2(Lb) 2· 0.5MeOH] n(3) and [Co(NCS) 2(Lc) 2·2H 2O] n(4), respectively. The X-ray diffraction analyses indicated that polymers 1-4 consist of a one-dimensional Co(II) chain in which each of the two adjacent Co(II) ions is bridged by two pyCO 2-(CH 2) m-O 2Cpy ligands to form a macrocycle. In addition, the structures of polymers 1-4 were also characterized by infrared spectroscopy, thermogravimetry and elemental analysis.

Synthesis,Structure and Theoretical Calculation of Metal Coordination Polymers with Pyrazine-2,3-dicarboxylic Acid and 3-(2-Pyridyl)pyrazole as Co-ligands

A new 2D metal coordination polymer(MCP),[Mn(pzdc)0.5(L)]n(1,pzdc=pyrazine-2,3-dicar-boxylic acid,HL=3-(2-pyridyl)pyrazole),was synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction,powder XRD,FT-IR,TG,fluorescence and elemental analysis techniques.Pale yellow crystals crystallize in orthorhombic system,space group Fdd2 with a=11.2368(6),b=38.280(2),c=10.5682(6)Å,V=4545.9(4)Å3,C11H7MnN4O2,Mr=282.15,Dc=1.649 g/cm3,μ(MoKα)=1.159 mm^(-1),F(000)=2272,Z=16,the final R=0.0613 and wR=0.1773 for 2856 observed reflections(I>2σ(I)).It shows a two-dimensional network structure and is further assembled into a three-dimensional supramolecular framework via hydrogen bonds and abundantπ-πinteractions.In addition,we analyzed natural bond orbital(NBO)of 1 in using the PBE0/LANL2DZ method established in Gaussian 03 Program.There is obvious covalent interaction between the coordinated atoms and Mn(Ⅱ)ions.

Synthesis, Structure and Luminescent Property of a 2D Cd(Ⅱ) Coordination Polymer Based on Mixed-ligands of 1,3-Bis(imidazol)propane and Pyridine-3,5-dicarboxylic Acid

A new Cd（Ⅱ） coordination polymer, namely, [Cd（1,3-bip）（3,5-pdc）]n （1,3-bip = 1,3-bis（imidazol）propane and 3,5-pdc = pyridine-3,5-dicarboxylic acid） has been synthesized under hydrothermal conditions. Compound 1 was characterized by infrared spectrum, elemental analysis, powder X-ray diffraction （PXRD） and single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/c with a = 1.40178（7）, b = 1.72502（12）, c = 1.41635（6） ran, β = 92.653（4）°, V = 3.4212（3） nm3, Z = 4, C16HIsCdNsO4, Mr = 453.73, Dc = 1.762 g/cm3, F（000） = 1808,μ = 1.310 mm1, R = 0.0899 and wR = 0.1945. In compound 1, each 3,5-pdc ligand links three Cd（lI） ions and each Cd（Ⅱ） attaches to bip ligands to form a complicated 2D double-layer structure. In addition, the thermal stability and luminescent property of 1 have been studied in the solid state at room temperature.

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＇-bipyri- dine-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.

Synthesis and Crystal Structure of a Three-dimensional Mn(Ⅱ) Coordination Polymer with 3-(Pyrazin-2-yloxy)-pyridine and Azide Anion as Mixed Bridge Ligand

A three-dimensional coordination polymer [Mn2（μ1.3-N3）4（μ-PP）2]n （PP = 3-（pyrazin-2-yloxy）-pyridine） has been synthesized with 3-（pyrazin-2-yloxy）-pyridine and azide anion as mixed bridge ligand, and its crystal structure was determined by X-ray crystallography. The crystal data： triclinic system, space group P1, with a = 6.794（4）, b = 9.885（6）, c = 9.947（6） A, α = 64.170（6）, β= 84.190（8）, γ= 85.319（8）°, V = 597.7（6）A^3, Z = 1, C18H14Mn2N18O2, Mr = 624.35, Dc = 1.735 g/cm^3, F（000） = 314 and μ = 1.117 mm^-1. In the crystal, the azide anion acts as a bridge ligand and makes adjacent Mn（Ⅱ） ions connect into a two-dimensional sheet on the ab plane, then 3-（pyrazin-2-yloxy）-pyridine serves as a bidentate bridge ligand to connect neighboring sheets along

Syntheses and Structures of Uwo New Oxalate-bridged Transition-metal Supramolecular Polymers of [M(2-NH_2py)_2(ox)]

Two new supramoleeular polymers [ M （2-NH2 py）2 （ox） ] [ M = Co （1）, Ni （2） ; 2-NH2py = 2-aminopyridine; ox = oxalate ] were hydrothermally synthesized and characterized by elemental analyses, IR and single-crystal X-ray diffraction analyses. The isomorphic compounds 1 and 2 both possess one-dimensional zigzag chain structures, which are composed of [ M （2-NH2 py）2 ]^2＋ units bridged by tetradentate oxalate ligands to form three-dimensional supramolecular network v/a the C-H…O hydrogen bonds and π-π stacking interactions. Compound 1 displays antiferromagnetie interaction.

Construction of a 3D Co(Ⅱ) Framework Based on Two Types of V-shaped Bidentate Ligands

A three-dimensional （3D） coordination polymer {[Co（bdc）（dpb）]·H2O}n （1） was prepared by solvothermal reaction of 1,3-dipyridyl benzene （dpb） with deprotonated 1,3-benzene- dicarboxylate （H2bdc）, and was characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. It crystallizes in the monoclinic system, space group C2/c with α = 15.478（6）, b = 12.865（5）, c = 24.091（10） ？, β = 95.599（5）°, V = 4774（3） ？3, C24H18CoN2O5, Mr = 473.34, Dc = 1.267 g/cm3, F（000） = 1864.0, μ = 0.748 mm-1 and Z = 8. Each Co（II） ion links three bdc2- anions to form an infinitely 1D ladder-shaped chain containing binuclear [（COO）Co]2 cluster, and dpb links adjacent 1D chains to form a 3D pcu framework. In addition, the UV-vis of 1 was also studied.

吡啶鎓类配位聚合物{[Zn(L)Cl_(2)]·4H_(2)O}的合成及结构研究

利用半刚性吡啶鎓多羧酸配体1,1’-([1,1’-联苯]-4,4’-二基双(亚甲基))双(4-羧基吡啶-1-鎓)(H2LCl)作为连接体,与Zn^(2+)离子在水热条件下加热至120℃反应72小时成功构筑出一例Zn(Ⅱ)配合物,即{[Zn(L)Cl_(2)]·4H_(2)O}。通过X-单晶衍射对其进行分析,{[Zn(L)Cl_(2)]·4H_(2)O}是一维链状结构,属于单斜晶系,P21/c空间群(晶胞参数a=15.951(6)A,b=9.636(4)A,c=18.849(7)A,α=90°,β=113.240(6)°,γ=90°)。Zn(Ⅱ)中心以四配位的模式连接两个羧基氧原子和两个Cl-离子形成一个有点扭曲的四面体构型。在配合物中,H2LCl配体含有能够旋转的-CH_(2)-基团和联苯的结构,-CH_(2)-基团使得两个吡啶环与联苯环不在同一个平面上且两个吡啶环的方向相反使得配体呈现出“Z”字型结构,更能够让配体参与配位。另外,联苯中的π共轭结构不仅让每个一维链状配合物通过π-π堆积作用进一步形成三维超分子,还能增加其结构的稳定性。

Synthesis and Characterization of a One-dimensional Coordination Polymer Generated from Unsymmetrical Bridging Organosulfur Ligand

A new one-dimensional（1D） coordination polymer [Zn（MMTA）2]n（MMTA=5-mercapto-l-methyl-tetrazole） was synthesized under solvothermal conditions and characterized by single crystal X-ray diffraction. This compound crystallizes in the monoclinic space group C2/c, with cell parameters： a=1.4938（7） nm, b=1.3599（5） nm, c=1.2180（4） nm, fl=120.84（3）^＊, V=2.1243（2） nm^3, and Z=8. The deprotonated HMMTA molecule as a/a2-1igand links the zinc center, forming ID chains, which are luther linked by weak C--H...N hydrogen bonds, forming a three-dimensional supramolecular framework. The compound exhibits intense photoluminescence at room temperature. On the basis of the results of TG/DTA analyses, the structure is thermally stable up to -280 ℃.

A Luminescent Cd(Ⅱ) Coordination Polymer Constructed from Isophthalic Acid and 1,3-Bis-(4-pyridyl)propane

A new coordination complex [Cd2（ip）2（bpp）]n （1, H2ip = isophthalic acid, bpp = 1,3-bis-（4-pyridyl） propane） has been synthesized and structurally characterized. Crystal data for the title complex are as follows： triclinic system, space group Pi with a = 9.6724（6）, b = 10.2243（6）, c = 14.8205（9） A, a = 88.927（5）, β = 71.664（6）, ）, = 75.767（5）°, F= 1345.79（14） A3, Mr = 751.29, Z= 2, F（000） = 740, Dc = 1.854 g/cm^3,μ（MoKa） = 1.636 mm^-1, R = 0.0259 and wR = 0.0623 for 4754 observed reflections with I 〉 20（0. X-ray structure analysis reveals that complex 1 holds a 3D architecture based on a-Po primitive cubic units with the [Cd4（COO）8] units treated as 6-connected nodes. Solid-state properties for 1, such as infrared spectroscopy, elemental analyses, thermal stability and luminescent property, have also been investigated.

Construction of a 2D Cd(II) Coordination Polymer Based on a V-shaped Bidentate Ligand

A two-dimensional（2D）coordination polymer{[Cd（bdc）（dpb）]·H2O}n（1）has been prepared by solvothermal reaction of 1,3-dipyridyl benzene（1,3-dpb）with deprotonated1,4-benzenedicarboxylate（H2bdc）,and was characterized by elemental analysis,IR spectroscopy,and X-ray single-crystal diffraction.It crystallizes in the monoclinic system,space group C2/c with a=15.1839（12）,b=20.7585（17）,c=7.2989（6）,β=117.3450（10）°,V=2043.5（3）3,C24H18N2O5Cd,Mr=526.81,Dc=1.712 g/cm3,F（000）=1056.0,μ=1.110 mm-1and Z=4.The neighboring Cd（II）ions link the bdc2-anions and 1,3-dpb to form an infinite 2D sheet,and such two2D sheets are interlocked with each other to form a 2D→2D sheet.Two groups of interlocked sheets are further linked together by intermolecularπ···πinteraction,giving a 3D supramolecular network.In addition,the fluorescence property of 1 was also studied.

A One-dimensional Coordination Polymer of Copper(Ⅱ) and Bis(4,6-dimethyl-2-pyrimidinethiolato)methane

Reaction of bis（4,6-dimethyl-2-pyrimidinethiolato）methane（bpytm） with CuCl2·4H2O in a mixed methanol/dichloromethane solution gave a one-dimensional coordina-tion polymer [CuCl2（μ-bpytm）]n which was characterized by single-crystal X-ray diffraction.It crystallizes in monoclinic,space group P21/c with a=16.9433（5）,b=13.6986（4）,c=7.8434（2）,β=100.371（2）°,V=1790.71（9）3,Z=4,Mr=426.86,Dc=1.583 g/cm3,μ（MoKα）=1.751mm-1,F（000）=868,S=1.025,the final R=0.0399 and wR=0.0924 for 2538 observed reflections with Ⅰ〉2σ（I） and 206 variables. The neutral coordination polymer is constructed by the bidentate thioether ligands to link adjacent copper atoms. Each copper atom is bridged by two adjacent nitrogen atoms of bpytm ligands and terminally bonded by two chloride atoms to form a squareplanar coordination geometry. The average Cu-N and Cu-CI bond lengths are 2.025（2） and 2.234（1） A, respectively.