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.

Hydrothermal Synthesis and Crystal Structure of a Manganese(II) Coordination Polymer with 1,1′-Biphenyl-2,2′,6,6′-tetracarboxyl Acid and 2,2′:6,2′′-Terpyridine Ligands

The title compound {[Mn（H2BPTC）（tpy）（H2O）]·（H2O）3}, （1, H4BPTC = 1,1＇- biphenyl-2,2＇,6,6＇-tetracarboxylic acid, tby = 2,2＇：6,2＇-terpyridine） has been synthesized by the hydrothermal reaction, and its structure was determined by X-ray diffraction and characterized by elemental analysis, IR spectrum and thermogravimetric analysis. The crystal is of monoclinic, space group P21/c with a = 10.971（2）, b = 20.776（4）, c = 14.332（3） A, β = 109.25（3）°, MnC31H27N3O12, Mr = 688.50, V= 3084.1（10） A^3, Dc = 1.483 g/cm^3, F（000） = 1420, p = 0.498 mm^-1, S = 1.066 and Z = 4. The final refinement gave R = 0.0447 and wR = 0.1103 for 5107 observed reflections with I 〉 2σ（I）. The title complex has a {[Mn（H2BPTC）（tpy）（H2O）]}, chain structure, and the hydrogen bonding interactions make it more stable. Each chain is further connected to the adjacent ones through π…π, C-H…π and rich hydrogen bonds to form a metal-organic coordination polymer.

A One-dimensional Pseudo-helical Coordination Polymer with 4,4′-(Hexafluoroisopropylidene)bis(benzoic acid)

The title complex [Zn2（hfipbb）2（2,2′-bpy）2], 1 has been hydrothermally synthesized from Zn（NO3）2·6H2O, 4,4′-（hexafluoroisopropylidene）bis（benzoic acid） and 2,2′-bipyridine. Singlecrystal X-ray analysis reveals that 1 presents a one-dimensional coordination polymer with pseudo-helical chain structure. Two Zn（Ⅱ） atoms in an unsymmetrical unit of 1 adopt distorted octahedral and square-pyramidal coordination geometries, respectively. The packing of parallel chains gives a three-dimensional supramolecular network supported by π-π stacking interactions. Crystal data： C54H32F12N4O8Zn2, Mr = 1223.58, monoclinic, space group P2 1/c, a = 27.557（6）, b = 16.751（3）, c = 11.350（2） A, β= 99.21（3）°, V= 5171.5（18） A^3, Z= 4, Dc = 1.572 g/cm^3, F（000） = 2464, μ= 1.030 mm^-1, the final R = 0.0552 and wR = 0.1070 for 6631 observed reflections （I〉 2σ（I））.

Synthesis,Crystal Structure and Fluorescence Property of the Ag(Ⅰ) Coordination Polymer Constructed by 2D[Ag(1,3-BIP)(PMA)_(0.5)]_n^(n-)Layers and 1D[Ag(1,3-BIP)(H_2O)]_n^(n+) Chains

A new AgO） coordination polymer, {[Ag（1,3-BIP）（H20）][Ag（1,3- BIP）（PMA）0.5.- 4H20}n （PMA = 1,2,4,5-benzenetricarboxylic acid, 1,3-BIP = 1,3-bis（imidazole）propane）, 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 the title complex is formed by 1D polymeric cationic chains of [Ag（1,3-BIP）（H2O）]n^n＋ and 2D polymetric anionic layer of [Ag（1,3-BIP）（PMA）0.5]n^n-, which are further linked by intermolecular H-bonding to form a 3D supramolecular framework. In addition, the photoluminescence property of the title complex in the solid state at room temperature was also investigated.

Synthesis, Crystal Structure and Electrochemical Properties of a One-dimensional Chain Coordination Polymer [Mn(NAA)_2(4,4’-bipy)(H_2O)_4]_n

A novel one-dimensional chain coordination polymer [Mn（NAAh（4,4′-bipy）（H2O）4], has been synthesized with a-naphthaleneacetic acid, 4,4′-bipy and manganese（Ⅱ） sulfate as raw materials. Crystal data for this complex： monoclinic, space group P21/c, a = 1.1421（2）, b = 1.6337（3）, c = 0.94177（19） nm, β = 112.15（3）°, V = 1.6275（6） nm^3, De = 1.407 g/cm^3, Z = 2, μ（MoKa） = 0.467 mm^-1, F（000） = 722, S = 1.007, R= 0.0412 and wR = 0.1022. The crystal structure shows that two neighboring manganese（Ⅱ） ions are linked together by one 4,4′-bipy molecule, and the whole complex molecule forms a one-dimensional chain structure. Each manganese（Ⅱ） ion is coordinated with two oxygen atoms of two a-naphthaleneacetic acid molecules, two nitrogen atoms of two 4,4′-bipy molecules and two oxygen atoms from two water molecules, giving a distorted octahedral coordination geometry. The electrochemical properties were also analyzed.

Synthesis, Crystal Structure and Electrochemical Properties of a One-dimensional Chain Coordination Polymer [Mn(phen)(2,4,6-TMBA)_2(H_2O)]_n

A one-dimensional chain-like coordination polymer [Mn（phen）（2,4,6-TMBA）2（H2O）]n has been synthesized from 2,4,6-trimethylbenzoic acid, 1,10-phenanthroline and anhydrous manganese（Ⅱ ） sulfate and then characterized. Crystal data for this complex： tetragonal, space group I41, a = 2.05643（16）, b = 2.05643（16）, c = 1.3939（2） nm, V = 5.8946（11） nm^3, Mr = 579.54, Z = 8, Dc = 1.306 g/cm^3, μ（MoKα） = 0.490 mm^-1, F（000） = 2424, S = 0.985, the final R = 0.0411 and wR = 0.0950. The Flack factor is -0.01（2）. The crystal structure shows that two neighboring man- ganese（Ⅱ ） ions are linked together by one bridge-chelating 2,4,6-trimethylbenzoic group, forming a one-dimensional chain structure. The manganese（Ⅱ ） ion is coordinated with two nitrogen atoms of one 1,10-phenanthroline, three oxygen atoms from three 2,4,6-trimethylbenzoic acids and one water oxygen atom, giving a distorted octahedral coordination geometry. The cyclic voltametric behavior of the complex was also investigated.

Synthesis and Crystal Structure of a New Mn(Ⅱ) Coordination Polymer Based on Asymmetric Semi-rigid V-shaped Dicarboxylate

A novel manganese（Ⅱ） coordination polymer with 2-（4-carboxyphenoxy） benzoic acid （2,4＇-H2oba） and 1,10-phenanthroline （1,10-phen） has been prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction, IR and elemental analysis. Compound [Mn（2,4＇-oba）（1,10-phen）] is of monoclinic system, space group P21/n with a = 7.960（1）, b = 15.464（2）, c = 18.703（3）A, β = 99.976（2）°, V = 2267.5（6） A^3, Z = 4, Mr = 491.35, Dc = 1.439 g/cm^3, F（000） = 1004 and μ = 0.623 cm·1. The final R = 0.0419 and wR = 0.0978 for 3444 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that the oba2-ligands adopt a bis（chelating bidentate） mode to link two Mn（Ⅱ） centers to form an infinite 1D helical chain. Furthermore, a 3D supramolecular structure was formed by π-π stacking interactions and hydrogen bonds.

One-dimensional Zigzag Chain Coordination Polymer [Zn(μ-phth)(imi)_2]_∞ Bridged by ο-Phthalato

The reaction of zinc carbonate with o-phthalic acid and imidazole in an aqueous-alcohol solution led to the formation of colorless crystals of [Zn(-phth)(imi)2]∞. Single-crystal X-ray analysis has revealed that the complex crystallizes in a monoclinic system, space group Pn with a = 8.394(2), b = 9.976(3), c = 9.959(3) ? ?= 104.409(4)? V = 807.6(4) ?, Z = 2, C14H12N4O4Zn, Mr = 365.65, Dc = 1.504 g/cm3, ?= 1.544 mm-1, F(000) = 372, the final R = 0.0466 and wR = 0.1171 for 1834 reflections with I >2(I). The complex displays a zigzag infinite chain structure in which each zinc (Ⅱ) center is coordinated by two oxygen atoms and two nitrogen atoms to generate a ZnN2O2 distorted tetrahedral geometry. The neighboring zinc atoms are bridged by the o-phthalate ligand. Each chain is linked by hydrogen bonds with its neighbors to form a three-dimensional coordination polymer.

A New Zn(Ⅱ) Coordination Polymer Constructed by 1,4-Benzenedithiolate Dianion: [Zn(SC_6H_4S)(1,3-DPA)]_n

A new one-dimensional polymer, [Zn（SC6H4S）（1,3-DPA）]n （1, SC6H4S = 1,4-ben- zenedithiolate and 1,3-DPA = 1,3-diaminepropane）, has been synthesized and characterized by elemental analysis, PXRD, IR spectra, and single-crystal X-ray diffraction. The complex crystallizes in triclinic system, space group P1, with a = 6.7119（1）, b = 9.0230（2）, c = 10.4943（2） A, a = 69.288（1）, β = 75.848（1）, ）, = 81.513（1）°, V= 575.123（19） A3, Dc = 1.615 g/cm^3, Z = 2, F（000） = 288; the final S = 1.070, R = 0.0234, and wR = 0.0551. The compound consists of an infinite zigzag chain formed by [Zn（1,3-DPA）]^2＋ units joined by SC6H4S ligands. Each chain interacts with neighboring chains via weak N-H…S hydrogen bonds to form an extended three-dimensional （3D） supramolecular network. The thermal and photoluminescent properties of 1 have also been investigated.

Structure and Photochemical Properties of a Chiral Cd Coordination Polymer Based on 4,4'-(Hexafluoroisopropylidene)Bis(benzoic acid)and 1,3-Di(pyridineyl)benzene

One new chiral metal-organic coordination polymer,[Cd2（dpb）（H2hfipbb）2]n,was obtained under hydrothermal conditions of 1,3-di（pyridineyl）benzene（dpb） and 4,4＇-（hexafluoroisopropylidene）bis（benzoic acid）（H2hfipbb）. The title compound reveals a three-dimensional（3D） framework with two types of helical chains [Cd（COO）]n,which are linked each other to further form a double helical chain [Cd2（COO）2]n by sharing the same Cd（Ⅱ） ions. The dpb connects the double helical chains to generate a 3D framework. These unique structures were studied by single-crystal X-ray and other spectroscopy techniques. In addition,the luminescent,fluorescence lifetime and second harmonic generation efficiency properties in the solid state have been studied.

Hydrothermal Synthesis and Crystal Structure of a New 2D Mn(II) Coordination Polymer with 4,4′-Sulfonyldi Benzoic Acid and 1,4-Bis(imidazol-1-ylmethyl) benzene Ligands

A novel manganese coordination polymer [Mn2（sfdb）2（biyb）2（H2O）2]n （1, H2sfdb = 4,4′-sulfonyldibenzoic acid, biyb = 1,4-bis（imidazol-1-ylmethyl）benze） has been hydrothermally synthesized and structurally characterized by single-crystal X-ray determination, IR and thermogravimetric analysis （TGA）. Complex 1 crystallizes in the triclinic system, space group Pi with a = 10.138（4）, b = 11.187（5）, c = 13.582（6） A, α = 69.146（7）, β = 89.628（7）, γ = 77.076（7）°, MnzC56H48N8O14S2, Mr= 1231.02, V= 1398.5（10） A3, Dc= 1.462 g/cm3, F（000） = 634,μ = 0.600 mm-1, S = 1.088 and Z = 1. The final refinement gave R = 0.0570 and wR = 0.1229 for 4889 observed reflections with 1 〉 2σ（I）. Interestingly, in complex 1, the sfdb2 and biyb ligands connect the Mn（Ⅱ） ions into two-dimensional 2-fold interpenetrating layers, and such layers are further connected with each other to generate a 3D supramolecular structure through hydrogen bonding interaction.

Syntheses, Structures and Properties of Two 2D Coordination Polymers from 5-(Pyridin-2-yl-methyl)aminoisophthalate

Hydrothermal reactions of 5-（pyridin-2-yl-methyl）aminoisophthalic acid（H2paip） with Mn（OAc）2·4H2O and Cu（NO3）2·3H2O produced two 2D complexes, [Mn（paip）]n·nH2O（1） and [Cu（paip）（H2O）]n（2）. In complex 1, paip serves as a μ4-bridge, and its two carboxylate groups in μ2,η2-bridging and chelating modes connect Mn（Ⅱ） into 1D chains, which are further extended into a 2D layer through coordination of two chelating nitrogen atoms. However, paip in complex 2 acts as a μ3-bridge to link Cu（Ⅱ） into a 2D layer, in which two carboxylate groups function in a monodentate mode, and hydrogen bonds between the coordinated water and carboxylate oxygen atoms further extend the 2D layers into a 3D supramolecular network. The frameworks of complexes 1 and 2 are stable up to 470 and 250 ℃, respectively. Magnetic measurement shows that complex 2 possesses a weak antiferromagnetic interaction.

A Novel Copper(II) Coordination Polymer with Figure-of-eight-shaped Channels Occupied by Flexible Monodentate and Bidentate N,N′-bipyrdyl Ligands

A copper（Ⅱ） coordination polymer, [Cu3（HOA）2（bpp）4]n （1, HnOA = 3,3＇,4,4＇- oxidiphthalic acid, bpp = 1,3-bis（4-pyridyl） propane）, has been hydrothermally synthesized. The crystal structure is of monoclinic, space group P21/c with a = 11.544（3）, b = 16.129（4）, c = 21.181 （6） A, β = 98.848（5）, V= 3897.0（2） A3, C84018N8H70Cu3, Mr = 1670.13, Z = 2, De = 1.423 g/cm^3, F（000） = 1722, μ = 0.887 mm^-1, R = 0.0878 and wR = 0.2583 for 8496 observed reflections （I 〉 2σ（I））. Single-crystal X-ray structural analysis reveals that 1 is a three-dimensional （3D） framework based on a two-dimensional （2D） mesomeric layer of alternating left- and fight-handed helical chains. The monodentate terminal and bidentate bridging bpp ligands in the same conformation are all encapsulated in the figure-of-eight-shaped channels, thus further stabilizing the whole three-dimensional framework.

Synthesis,Structure and Property of a 1D Coordination Polymer [Mn{5-(NO_2)sal}2_(phen)]_n with 5-Nitrosalicylate Ligand

A new coordination polymer [Mn{5-（NO2）sal}2（phen）]n （5-（NO2）sal = 5-nitrosalicylate, phen = 1,10-phenanthroline） was synthesized by a hydrothermal reaction and characterized by elemental analysis, IR and X-ray single-crystal diffraction. The title complex crystallizes in orthorhombic, space group Pbcn with α = 25.747（8）, b = 13.220（4）, c = 7.009（3） A, V= 2386（1）A^3, Z = 4, R = 0.0427 and wR = 0.0890. The 5-nitrosalicylate anions doubly bridge the Mn（Ⅱ） atoms to form a one-dimensional polymeric chain with repeated eight-membered ring units （Mn-O-C-O）2. The crystal structure is stabilized by intra- and interchain hydrogen bonding interactions. The cyclic voltammetric behavior of the title complex is also reported.

Homochiral Coordination Polymers from Single Helices to Multiple Helices Controlled by Metal Ions

Helix as essential molecular chiral phenomenon at supramolecular level offers an affective method to study chiral characteristic of homochiral coordination polymers(CPs).Herein,two homochiral CPs[Cd((R)-CBA)_(2)(3,5-DIT)]_(n)((R)-H_(2) CBA=(R)-4-(1-carboxyethoxy)benzoic acid,3,5-DIT=3,5-di(1 H-imidazol-1-yl)toluene,1-R)and[Zn((R)-CBA)(3,5-DIT)]_(n)(2-R)were synthesized under hydrothermal conditions.In complex 1-R,only a helical chain was built by chiral ligands(R)-CBA2-,ancillary ligands 3,5-DIT and Cd(Ⅱ)ions.After Cd(Ⅱ)ions were replaced by Zn(Ⅱ)ions under similar reaction system,Zn(Ⅱ),(R)-CBA^(2-)and/or 3,5-DIT formed six types of helices,resulting in complex 2-R.So,the metal ions played a key role in the construction of helical structures.Complexes 1-R and 2-R were also characterized by elemental analysis,PXRD,TGA,CD and UV-visible absorptions.In addition,complexes 1-R and 2-R exhibited different photoluminescence behaviors in solid sate compared to free ligand(R)-H_(2)CBA.

Assembly of Two Coordination Polymers Based on 2,2 ＇-Bipyridyl-4,4＇-dicarboxylic Acid Ligand

Two novel 2D coordination polymers, [Co（BPDC）DMSO]·DMSO（1）（BPDC=2,2＇-bipyridyl-4,4＇-dicar- boxylic acid） and [Zn（BPDC）DMF]·DMF（2）, were synthesized from 2,2＇-bipyridyl-4,4＇-dicarboxylic acid ligand （H2BPDC） under solvothermal conditions. Single crystal X-ray diffraction analyses reveal that compound 1 crystal- lizes in orthorhombic system and Pca21 space group with a=1.29628（13） nm, b=1.13721（13） nm, c=1.66457（19） nm, α=90°, β=90°, γ=90°, V=2.4538（5） nm3. Compound 2 crystallizes in monoclinic system and P21/c space group with a=0.9429（6） nm, b=1.4757（10） nm, c=1.5980（9） nm, α=90°, β=114°, γ=90°, V=2.030（2） nm3. Compounds 1 and 2 exhibit two different 3-connected hcb and fes topologies, respectively. The structures of the two compounds both contain interesting characters of double-helical chains（left- and right-handed helical chains）. Additionally, the mag- netic and luminescent properties of the two compounds were studied.

两个Mn(Ⅱ)/Co(Ⅱ)配位聚合物的脲热合成、结构和荧光性质

通过脲热合成法合成了2个金属配位聚合物[Mn3(Hidc)3(DMI)2]n(1)(H3idc=4,5-咪唑二羧酸,DMI=1,3-二甲基-2-咪唑啉酮),[Co(tbip)(DMPU)]n(2)(H2tbip=5-叔丁基间苯二甲酸,DMPU=N,N-二甲基丙烯基脲)。通过元素分析、红外光谱、X射线粉末衍射、单晶X射线衍射等对配合物进行了结构表征。结果表明:配合物1属单斜晶系,空间群为P21/n。该配合物以DMI为模板剂,通过H3idc与Mn(Ⅱ)构筑成三维四方孔道结构,DMI填充在孔道中。配合物2属单斜晶系,空间群为P21/c。该配合物以DMPU为模板剂,通过H_2tbip与Co(Ⅱ)构筑成二维网状结构,DMPU分子通过与Co(Ⅱ)配位填充在网格中。固体荧光性能测试表明配合物1在462 nm处存在较强的荧光发射峰,说明具有良好的蓝光性质。

以2,2′-联吡啶-4,4′-二甲酸和2-甲基吡嗪[3,2-f:2′,3′-h]喹喔啉为配体的三维锰(Ⅱ)配位聚合物的合成、晶体结构和荧光性质(英文)

采用水热法合成了一个锰的配合物[Mn(bpydc)(Medpq)]n(1)(H2bpydc=2,2′-联吡啶-4,4′-二甲酸,Medpq=2-甲基吡嗪[3,2-f:2′,3′-h]喹喔啉),并利用元素分析、红外光谱、紫外可见光谱、热分析和X-射线单晶衍射对其结构进行了表征。单晶结构分析表明配合物1属于单斜晶系,Cc空间群,晶胞参数a=2.031 6(4)nm,b=1.564 5(3)nm,c=0.719 26(14)nm,β=103.97(3)°,V=2.218 5(8)nm3,Z=4。配合物1是一个锰(Ⅱ)离子经由bpydc2-连接形成的三维网络结构。配合物1的固体荧光光谱表明它具有很强的荧光性。应用Gaussian 03W程序,在HF/LANL2DZ水平上对标题化合物的自然键轨道(NBO)进行了分析,结果表明Mn(Ⅱ)与配位原子间的价键类型都属于共价键范畴。

四配位Co(Ⅱ)构建的螺旋配位聚合物:合成、结构和对CO2的光催化还原

在水热条件下,对映的乳酸衍生物(R)-4-(1-羧基乙氧基)苯甲酸((R)-H2CBA)和(S)-4-(1-羧基乙氧基)苯甲酸)((S)-H2CBA)分别与辅助配体1,3-双(2-甲基-1H-咪唑-1-基)苯(1,3-BMIB)以及Co(Ⅱ).反应,合成出一对结构新颖的金属-有机框架化合物{[Co((R)-CBA)(1,3-BMIB)]·H2O}n(1-D)和{[Co((S)-CBA)(1,3-BMIB)]·H2O}n(1-L)。单晶解析揭示在二维的1-D和1-L中,四配位的Co(Ⅱ).中心分别与乳酸衍生物(R)-H2CBA(或(S)-H2CBA)和/或1,3-BMIB一起构建出了3种不同结构的螺旋链。这对螺旋二维化合物在不同pH值的水中有一定的稳定性。紫外-可见吸收光谱显示1-D对420~650 nm范围的可见光有较强的吸收。进一步的Mott-Schottky测试表明1-D是典型的n型半导体。此外其较小的阻抗半径显示其有利于电子传输。在进一步的光催化实验中,1-D实现了光照条件下CO2转化为CO,反应平均速率为577.8μmol·g-1·h-1。

含有双螺旋链的配位聚合物[Co(dpa)prz_(0.5)]_n的合成、晶体结构及磁性质(英文)

A coordination polymer [Co(dpa)prz0.5]n(1) with double-helix chains has been constructed hydrothermally using H2dpa(H2dpa=diphenic acid),prz(prz=piperazine) and Co(NO3)2.6H2O.The structure and magnetic properties of the complex were investigated.The complex crystallizes in triclinic system and P1 space group.Each Co atom is five-coordinated and takes a distorted tetragonal pyramid geometry.Two carboxylates of the H2dpa ligands bridge four Co(Ⅱ) ions to form infinite right-handed or left-handed helical-C-O-Co-chains.The two types of helical chains are interconnected to each other through the Co (Ⅱ) centers to produce double-helix chains.The chains form a 2D sheet through the coordination interaction of prz molecules between adjacent chains.The sheets are further interlinked by hydrogen bond interactions to generate 3D coordination frameworks.Magnetic studies for complex 1 show stronger antiferromagnetic coupling between the Co(Ⅱ) ions.