Two Cadmium(II) Coordination Polymers from Flexible Bis(imidazolyl) Ligands

The hydrothermal reaction of 1,4-bis（imidazol-1-yl）butane （bimb） and 1,4-bis（2- methylimidazol-1＇-yl）butane （bmib） with CdBr2·4H2O gave rise to two coordination polymers, [Cd（bimb）2Br2]n （1） and [Cd（bmib）Br2]n （2）, respectively. Single-crystal X-ray diffraction analysis reveals that 1 and 2 crystallize in the monoclinic space group P21/n and the orthorhombic space group Pccn, respectively. In 1, bimb adopts an anti-anti-anti conformation and bridges adjacent Cd（Ⅱ） to form a two-dimensional （2D） network containing rhombohedral rings. The 2D layers are arranged in an offset ABCABC sequence to fill large void in the rhombohedral rings. In 2, bmib also exhibits an anti-anti-anti conformation, but it links neighboring Cd（Ⅱ） into a one-dimensional （1 D） chain. Br in 1 and 2 serves as a monodentate ligand to balance charge.

Topology and Photoluminescence Property of a Neodymium-carboxylate Coordination Polymer Based on a Tripodal Flexible Ligand

A new metal-organic coordination polymer {[Nd（tci）（H2O）2]·2H2O}n（1） has been synthesized based on the flexible tricarboxylate ligand tris（2-carboxyethyl）isocyanuric acid（H3tci） and structurally characterized by single-crystal X-ray diffraction analyses, elemental analysis, infrared spectra（IR）, powder X-ray diffraction（PXRD） and thermogravimetric analysis（TGA）. Complex 1 crystallizes in triclinic, space group P1 with a = 9.1648（11）, b = 9.3326（12）, c = 12.440（2） , C（12）H（20）N3O（13） Nd, Mr = 558.55, V = 886.9（2） 3, Z = 2, Dc = 2.092 g·cm-3, μ = 3.006 mm-1, F（000） = 554, 2.56〈θ〈25.00°, λ（Mo Kα） = 0.71073 , T = 293（2） K, the final R = 0.0662 and w R = 0.2071. X-ray diffraction analysis reveals that complex 1 is a two-dimensional layer, which is further assembled into a three-dimensional supramolecular architecture through hydrogen bonding interactions. The structure of complex 1 can be simplified as a rare 2-periodic uninodal {48·62} topology and a non-interpenetrating kgd topology. Furthermore, the thermal stability and photoluminescence property of 1 were investigated.

Synthesis, Structure and Slow Magnetization Relaxation of Co(Ⅱ) Complexes from a Flexible Imidazole-based Ligand

The employment of a flexible imidazole-based ligand(H_2L), condensed from 1 Himidazole-2-carbaldehyde and 1,2-bis(aminooxy)ethane, and Co^(2+) salt has led to the formation of Co(Ⅱ) complexes [Co(H_2L)_2Cl]Cl·4CH_3OH(1) and [Co(H_2L)(NCS)_2]_2·2C_4H_(10)O(2), in the presence of different anions, i.e, Cl-and SCN-, respectively. Single-crystal X-ray analyses show that complex 1 with a square pyramid(C_(4v)) local environment exhibits a two-dimensional(2D)layered(4,4)-net framework and complex 2 displays a dinuclear molecule box with a T_d local environment. By comparison between complexes 1 and 2, the versatile configuration of ligand including cis-and trans-form isomer has a significant effect on the structures of the resulting complexes. The magnetic properties of 1 and 2 are also investigated. The ac magnetic susceptibility revealed that 2 exhibits the characteristic of slow magnetization relaxation.

The Effects of Metal Ions and Secondary Ligands on the Formation of Structures Resulted from Flexible Building Blocks

Two coordination polymers have been synthesized from cpg/4,4＇-bipy/metal ions reaction system, [Zn（cpg）（4,4＇-bipy）0.5（H2O）]·H2O 1 and [Cd（cpg）（4,4＇-bipy）0.5（H2O）2]·H2O 2. X- ray analyses show that different coordination geometries of zinc and cadmium ions lead to similar ladder structures （tetra-for zinc ion and hexa- for cadmium ion）, in which all the flexible cpg molecules exist as single conformations of anti-form.

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.

Syntheses and Crystal Structures of Two One-dimensional Cobalt(Ⅱ) Compounds with the Flexible Dipyridyl Ligand

Two one-dimensional cobalt（II） compounds {[Co（Hbpma）（H20）4]2·3SO4·4.5H2O}n 1 and {[Co（Hbpma）（NCS）3（H20）]·2.85H2O}n 2 （bpma = N,N＇-bis（3-pyridylmethyl）amine） have been synthesized and structurally characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group Pi with a = 15.8780（5）, b = 16.2187（5）, c = 16.4858（5） A, α = 91.0420（10）,β = 94.5190（10）, γ = 101.4360（10）°, V = 4145.7（2） A3, C24H53Co2N6024.5083, Mr = 1031.76, Z = 4, Dc = 1.653 g/cm3, p（MoKa） = 1.046 mm-1, F（000） = 2148, S = 1.017, the final R = 0.0269 and wR = 0.0644 for 13032 observed reflections （I 〉 2a（/））. For complex 2, it belongs to triclinic, space group Pi with a = 9.3761（11）, b = 10.5814（13）, c = 11.2972（14）A, α= 85.472（2）,β = 88.058（2）,γ = 76.203（2）°, V= 1085.0（2） A3, C15Hzl.v0CoN603.85S3, Mr= 502.79, Z = 2, Dc = 1.539 g/cm3, p（MoKa） = 1.112 mm-1, F（000） = 519, S = 1.070, the final R = 0.0358 and wR = 0.0899 for 3466 observed reflections （I 〉 2σ（I））. Two complexes 1 and 2 are both found to be one-dimensional coordination polymers bridged by the protonated bpma ligands, which are assembled into three-dimensional supramolecular structures through the hydrogen bonding interactions and π-π packing interactions.

Anion Directed Assembly of Cu(Ⅱ)Complexes Formed by a Flexible Ligand

Coordination polymers,consisting of metal,anion and organic ligands,have attracted much attention.The structure of coordination polymers is affected by various factors.To investigate the effects of anion,syntheses and structures of four Cu(II)complexes,namely[(Cu LCl)(PF)](1),[(Cu LCl)(ClO)](2),[(Cu LCl)?CHOH](3)and Cu LCl(4),are reported based on a flexible ligand,1,3-bis(2-pyridylmethyl)imidazolium(L).The ligand is accommodative to kinds of anions,and forms 1-D chains generally upon reaction with Cu(II)salts.The effect is measured by the conformational variation through the dihedral angles between different aromatic rings of the ligand.In order to further investigate the effect of anion,a protonated sample of L,namely,LH(ClO)?HO(5)is also synthesized and structurally characterized,showing an intriguing hydrogen bonded helix.

Syntheses,Structures,and Properties of Three New Polymers Based on Flexible and Rigid Ligands

Three new supramolecular polymers, [（IP）（H2SO4）（H2O）]（1）, [（H2SDC）（BPA）]（2） and [Mn（SDC）（IP）2]n （3）, have been constructed by three modes（rigid IP, rigid SDC ＋ flexible BPA, rigid IP ＋ rigid SDC）. Polymers 1 and 2 are supramolecular structures, assembled by hydrogen bonds and π···π interactions. X-ray structure analysis of 3 shows waved 1D chains which form a 3D supramolecular network by hydrogen bonds and π···π interactions. Solid-state properties of thermal stability, luminescent properties, and X-ray powder diffractions for these crystalline materials have also been investigated, and polymer 3 is considered to be a good stable luminescence material.

Syntheses,Structures and Properties of Two New Coordination Polymers with Flexible Ligands as Linkers

Two new coordination polymers,[ZnL1]n（1,H2L1 = 5-（4-pyridyl）-methoxyl isophthalic acid） and[Ni（L2）2（H2O）4]n（2,HL2 = 4-（pyridin-4-ylmethoxy）benzolic acid）,have been synthesized and characterized by elemental analysis,PXRD,IR spectra,and single-crystal X-ray diffraction.Compound 1 has a three-dimensional framework constructed by 6-bridged L1^2- anions connecting the Zn2（O2C）4 paddlewheel-like units.Compound 2 contains a mononuclear molecular unit,and the central nickel atom adopts a slightly distorted octahedral geometry by two nitrogen atoms from different L2^- ligands and four oxygen atoms from water molecules.These molecular units link each other via four types of O-H…O hydrogen bonds to form an extended three-dimensional（3D） supramolecular network.The thermal and photoluminescent properties of 1 and 2 have also been investigated.

Syntheses,Crystal Structures and Properties of Two New Compounds from a Flexible Bipodal Acid with Additional Amide Groups

Two novel compounds {[Cu（IBG）（4,4-bipy）（H2O）2]2·11H2O}n（1） and {[Co（IBG）-（μ-H2O）（H2O）2]·2H2O}n（2） based on isophthaloylbisglycine（H2IBG） have been synthesized and structurally characterized by thermogravimetric analysis, elemental analysis and single-crystal X-ray diffraction. Compound 1 shows a 1D chain sine/cosine chain structure, and compound 2 can be characterized as a 4-connected sql tetragonal planar network with the point symbol of {44·62}. Compound 2 has been characterized by magnetic measurements. In addition, 1 and 2 display an interesting reversible crystal-to-amorphous transformation.

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.

柔性二羧酸过渡金属配位聚合物的合成、表征和荧光性质

在溶剂热条件下,柔性二羧酸配体2,2'-(1,2-亚苯基双(亚甲基))双(硫二基)二尼古丁酸(H_(2)L)和1,10-菲咯啉(phen)与不同金属盐反应合成了6个新颖的配位聚合物:[Mn(L)(phen)(H_(2)O)]_(n)(1)、[Co(L)(phen)(H_(2)O)]_(n)(2)、[Cu(L)(phen)(H_(2)O)]_(n)(3)、[Zn_(2)(L)_(2)(phen)2(H_(2)O)]_(n)(4)、[Zn(L)(phen)]_(n)(5)和[Cd(L)(phen)2]_(n)(6)。对配合物1~6进行了单晶X射线衍射、元素分析、红外光谱、热重分析、粉末X射线衍射等测试和表征。1~6的单晶结构为不同的一维链,且能通过氢键作用链接形成三维超分子结构。其中1和2同构且L2-呈现顺式构象,3~6中L2-呈现反式构象。此外,研究了配合物4~6的荧光性质。

柔性三嗪含硫多羧酸Cu(Ⅱ)/Fe(Ⅲ)配合物的合成

三聚硫氰酸与3-氯丙酸反应得到1个具有3个丙酸基的柔性羧酸配体2,2',2″-[1,3,5-三嗪-2,4,6-三(硫代)]三丙酸(H_(3)TTPA),利用该配体分别与硝酸铜和硝酸铁反应,通过一步沉淀法,得到2个配合物(Cu-TTPA和Fe-TTPA)。通过X射线光电子能谱(XPS)、红外光谱(FTIR)、热分析(TG)对配体和配合物进行了结构表征,测定了2个配合物在不同pH值缓冲溶液中的稳定性及电导率。为柔性三嗪含硫多羧酸配体合成配合物的进一步研究提供了基础。

Two Interpenetrated Dia-type Coordination Polymers Constructed from Mixed Dicarboxylate and Bis(imidazol)-based Ligands

Two novel interpenetrating diamond frameworks, namely [Cd（mal）（bix）]n （1）and {[Zn（sub）（bib）]n.H2O}. （2）（H2mal = maleic acid, H2sub = suberic acid, bix = 1,4-bis（imidazol- l-ylmethyl）-benzene, bib = 1,4-bis（N-imidazolyl）butane） were hydrothermally synthesized and characterized by elemental analysis, infrared spectra （IR）, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis reveals that compound 1 crystallizes in the orthorhombic system with space group Pnma and features a 3-fold interpenetrating diamond framework. Compound 2 exhibits a 4-fold interpenetrating diamond network. The luminescent properties of these two compounds have also been investigated in detail.

Synthesis,Crystal Structure and Properties of a Novel Decavanadate Complex with One-dimensional Chain Involving Sodium and 'Bis-tris' Ligand

By using a flexible multidentate ligand,bis（2-hydroxyethyl）iminotris（hydroxyhydroxylmethy）methane（＇bis-tris＇：H5L）,the title complex {[Na（H6L）2]2}n·nV10O28（1） has been successfully synthesized under self-assembly condition and characterized by IR spectroscopy,elemental analysis,PXRD and single-crystal X-ray diffraction.The crystal structure belongs to an orthorhombic system,space group Cmca with a = 23.752（2）,b = 13.5360（8）,c = 18.5377（11） ,V = 5960.1（7）,Z = 8,Dc = 2.055 g/cm3,F（000） = 3744,μ = 1.630 mm-1,the final R = 0.0283 and wR = 0.0759 for 3353 observed reflections with I 〉 2σ（I）.This complex consists of decavanadate [V10O28]6-motifs as counter anions intercalated with one-dimensiond chains of the composition [Na（H6L）2]n3n＋.And significant intermolecular O-H…O hydrogen-bonding interactions lead to a three-dimensional supramolecular framework.

Two Discrete Cu-Complexes Constructed from a Multidentate N-Containing Dinucleating Ligand

Two comparable discrete complexes [CuⅡ（CH3CN）2L2]·2（ClO4） 1 and [CuI2I2L2]·（DMF）2 2 were successfully synthesized by the reaction of CuⅡ and CuⅠ salts with a novel dinucleating ligand 2,5-bis（3-pyridinylmethylthio）-1,3,4-thiadiazole）（L）,respectively.Complex 1 presents a single nuclear structure while 2 has a dimeric structure where two CuI ions are doubly bridged by halide ions in a μ2-fashion.Both discrete molecules were outspreaded into a one-dimensional supramolecular chain via aromatic interactions such as C–H…π and π…π interactions.

Two Copper-organic Frameworks Constructed from the Flexible Dicarboxylic Ligands

Two new copper-organic frameworks [Cu4(L^1)4(DMF)4·2DMF]n(DZ-1) and [Cu(L^2)(DMF)]n(DZ-2)(H2L^1 = 2,2'-(1,4-phenylenebis(methylene))bis(sulfanediyl)dinicotinic acid and H2L^2 = 2,2'-(1,2-phenylenebis(methylene))bis(sulfanediyl)dinicotinic acid) have been synthesized and characterized. DZ-1 with a zero-dimensional structure crystallizes in monoclinic crystal system, space group P21/n with a = 17.1697(11), b = 17.1241(11), c = 18.8638(14) ?, V = 5193.2(6) ?~3, Z = 2, Dc = 1.493 g·cm^(-3), μ = 1.046 mm^(-1), F(000) = 2408. All L^1 ligands adopted syn-conformation. DZ-2 is a two-dimensional structure crystallized in monoclinic crystal system, space group P21/n with a = 11.855(5), b = 18.601(8), c = 12.319(5) ?, V = 2400.4(18) ?~3, Z = 4, Dc = 1.514 g·cm^(-3), μ = 1.124 mm^(-1), F(000) = 1124. The selective sorption of CO2 over N2 for DZ-1 was found.

A series of coordination polymers constructed from flexible bis(benzimidazole)ether ligands and different carboxylates

Six new coordination polymers constructed from two structurally related ligands, 2,2′-bis(2-methylbenzimidazole) ether (L1) and 2,2′-bis(2-ethylbenzimidazole)ether (L2), have been synthesized. They are [Cu(L1)(bz)2] (1), [Cu(L2)(bz)2] (2), [Zn2(L1)(m-bdc)2] (3), [Cd2(L2)(m-bdc)2(H2O)]2·H2O (4), [Zn(L1)(OH-bdc)-(H2O)] (5) and [Zn2(L2)(btca)] (6), where Hbz = benzoic acid, m-H2bdc = 1,3-benzenedicarboxylic acid, OH-H2bdc = 5-hydroxyisophthalic acid, and H4btca = 1,2,4,5-benzenetetracarboxylic acid. In 1 and 2, the bidentate N-donor ligands (L1 and L2) bridge neighboring metal centers to form 1D single chains. The bz anions are attached on both sides of the chains. In 3 and 4, the N-donor ligands (L1 and L2) in cis conformations bridge two metal centers to generate a [M2(L1)]4+ unit (M = Zn(II) and Cd(II)). The adjacent [M2(L1)]4+ units are further linked via the dicarboxylate anions to form 1D double chain structures. In 5, the Zn(II) cations are bridged by OH-m-bdc anions to form an infinite polymeric chain. The L1 ligands are attached on one side of the chain in a monodentate mode. In 6, two Zn(II) cations are bridged by two L2 ligands to form a [ZnL2]2 4+ ring, which is further linked by btca anions to generate a 2D layer. The luminescent properties of the ligands and 3–6 in the solid state at room temperature were also studied.

Substituent groups from aromatic dicarboxylates modulated structural diversification in the assembly of Co(Ⅱ)complexes based on the bis-pyridyl-bis-amide ligands

Four coordination polymers based on two bis-pyridyl-bis-amide ligands and three aromatic dicarboxylates with different substituent groups, namely, [Co（3-bpcb）x.5（NPH）（H20）]＂ 4H20 （1）, [Co（3-bpcb）（NIPH）] （2）, [Co（3-bpcb）0.5（5-H2AIP）]＂ 2H20 （3）, [Co（3-bpcd）0.5（5-H2AIP）（H20）]＂ 2H20 （4） [3-bpcb = N,N＇-bis（3-pyridinecarboxamide）-l,4-benzene, 3-bpcd = N,N＇-bis（3- pyridine）cyclohexane-l,4-dicarboxamide, H2NPH = 3-nitrophthalic acid, H2NIPH = 5-nitroisophthalic acid, 5-HaAIP = 5-aminoisophthalic acid] have been synthetized under hydrothermal conditions. Complex 1 displays a one dimensional （1D） chain based on the binuclear [Co2（NPH）2] units and 3-bpeb ligands, which is extended into a three dimensional （3D） supra- molecular framework through hydrogen bonding and n-n stacking interactions. In complex 2, the （3,5）-connected two dimen- sional （2D） layers are constructed from 1D Co-NIPH chains and bidentate-bridging 3-bpeb ligands. Complex 3 is a 2D double layer based on Co-5-H2AIP 2D layers and 3-bpeb pillars. Complex 4 also displays a 2D network, which is constructed from the Co-5-H2AIP 1D double chains and 3-bpcd ligands. Finally, complexes 2--4 are extended into 3D supramolecular frame- works by hydrogen bonding or n-re stacking interactions. The substituent groups of dicarboxylates play an important role in the assembly and structures of the title complexes. In addition, the fluorescent properties of complexes 1-4 and the electrochemi- cal behaviors of 3 and 4 at room temperature have been investigated.

Construction of [Cu_nI_n]-based coordination polymers via flexible benzimidazolyl-based ligands

Four new [CunIn]-based coordination polymers, [{Cu4(μ3-I)4(mbbm)2}·2DMF]n (1), [(CuI)2(mbbm)2]n (2), [{Cu2(μ-I)2-(ebbm)2}·2MeCN]n (3), and [Cu2(μ-I)2(prbbm)2]n (4), were prepared from solvothermal reactions of CuI with three flexible ligands [(bzim)(CH2)n(bzim)] (bzim = benzimidazole; n = 1, mbbm; n = 2, ebbm; n = 3, prbbm). These compounds were characterized by elemental analysis, IR and X-ray crystallography. 1 consists of cubanelike [Cu4(μ3-I)4] fragments that link the neighboring ones via mbbm bridges to form a 1D ladder-type chain. 2 contains mononuclear [CuI] fragments that are bridged by mbbm ligands to yield a 1D zigzag chain. 3 or 4 contains a [Cu2(μ-I)2] dimeric fragment, which works as a four-connecting node to link its four equivalent ones to form a 2D (4,4) network (3) or acts as a two-connecting node to connect its two equivalent ones via two pairs of prbbm bridges to form a 1D double chain (4). The photoluminescent properties of 1-4 in the solid state at ambient temperature were investigated.