Syntheses,structures and properties of four metal-organic frameworks from chlorophenyl imidazole dicarboxylates

Four metal-organic frameworks, [Sr(o-ClPhHIDC)(H₂O)₂]_n (o-ClPhH₃IDC = 2-(o-chlorophenyl)-1H-imidazole-4,5-dicarboxylic acid) (1), [Mg(m-ClPhHIDC)(H₂O)₂]_n (2), [Sr(m-ClPhHIDC)(H₂O)]_n (3) and {[Co₃(m-ClPhIDC)₂(H₂O)₆]·2H₂O}_n (m-ClPhH₃IDC = 2-(m-chlorophenyl)-1H-imidazole-4,5-dicarboxylic acid) (4), have been solvothermally synthesized and structurally characterized. Single-crystal X-ray analyses reveal that 1–3 show 2-D architectures and 4 exhibits a 3-D structure. The o-ClPhH₃IDC and m-ClPhH₃IDC ligands in the polymers can be partly deprotonated and coordinate to metal ions by various modes. The metal ions of 1–4 are coordinated only to oxygens. The thermal and luminescence properties of the polymers have also been investigated.     

Charge-transfer host system composed of 9,10-bis(3,5-dihydroxyphenyl)anthracene and methylviologen

By using 9,10-bis(3,5-dihydroxyphenyl)anthracene as an electron donor and 1,1′-dimethyl-4,4′-bipyri-dinium dichloride as an electron acceptor, a spontaneously resolved charge-transfer (CT) complex is formed. This CT complex can include n-alkyl alcohol molecules as guests, and the DRS of this CT complex change with the type of component guest molecules.     

Syntheses, structures and photoluminescence of a series of coordination frameworks based on dicarboxylate anion and bis(imidazole) ligand

In this article, ten new coordination frameworks, namely, [Ni(H₂O)₆]·(L3) (1), [Zn(L3)(H₂O)₃] (2), [Cd(L3)(H₂O)₃]·5.25H₂O (3), [Ag(L1)(H₂O)]·0.5(L3) (4), [Ni(L3)(L1)] (5), [Zn(L3)(L1)_0.5]·H₂O (6), [Cd(L3)(L1)_0.5(H₂O)] (7), [CoCl(L3)_0.5(L1)_0.5] (8), [ZnCl(L3)_0.5(L2)_0.5] (9), and [CoCl(L3)_0.5(L2)_0.5] (10), where L1 = 1,1′-(1,4)-butanediyl)bis(imidazole), L2 = 1,1′-(1,4-butanediyl)bis(2-ethylbenzimidazole) and H₂L3 = 3,3′-(p-xylylenediamino)bis(benzoic acid), have been synthesized by varying the metal centers and nitrogen-containing secondary ligands. These structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses and IR spectra. In 1, the L3 anion is not coordinated to the Ni(II) center as a free ligand. The Ni(II) ion is coordinated by water molecules to form the cationic [Ni(H₂O)₆]²⁺ complex. The hydrogen bonds between L3 anions and [Ni(H₂O)₆]²⁺ cations result in a three-dimensional (3D) supramolecular structure of 1. In compounds 2 and 3, the metal centers are linked by the organic L3 anions to generate 1D infinite chain structures, respectively. The hydrogen bonds between carboxylate oxygen atoms and water molecules lead the structures of 2 and 3 to form 3D supramolecular structures. In 4, the L3 anion is not coordinated to the Ag(I) center, while the L1 ligands bridge adjacent Ag(I) centers to give 1D Ag-L1 chains. The hydrogen bonds among neighboring L3 anions form infinite 2D honeycomb-like layers, in the middle of which there exist large windows. Then, 1D Ag-L1 chains thread in the large windows of the 2D layer network, giving a 3D polythreaded structure. Considering the hydrogen bonds between the water molecules and L3 anions, the structure is further linked into a 3D supramolecular structure. Compounds 5 and 7 were synthesized through their parent compounds 1 and 3, respectively, while 6 and 9 were obtained by their parent compound 2. In 5, the L3 anions and L1 ligands connect the Ni(II) atoms to give a 3D 3-fold interpenetrating dimondoid topology. Compound 6 exhibits a 3D three-fold interpenetrating α-Po network structure formed by L1 ligands connecting Zn-L3 sheets, while compound 7 shows a 2D (4,4) network topology with the L1 ligands connecting the Cd-L3 double chains. In compound 8, the L1 ligands linked Co-L3 chains into a 2D layer structure. Two mutual 2D layers interpenetrated in an inclined mode to generate a unique 3D architecture of 8. Compounds 9 and 10 display the same 2D layer structures with (4,4) network topologies. The effects of the N-containing ligands and the metal ions on the structures of the complexes 1-10 were discussed. In addition, the luminescent properties of compounds 2-4, 6, 7 and 9 were also investigated.     

Syntheses,structures, and properties of two- and three-dimensional coordination polymers based on bis(imidazole) and glutarate ligands

Two new coordination polymers, [Zn(bix)_0.5(glu)]_n (1) and {[Co(bix)(glu)]·4H₂O}_n (2), were synthesized (bix = 1,4-bis(2-methylimidazol-1-ylmethyl)benzene, glu = glutarate). In 1, each Zn(II) is connected by four glu ligands and extend to form a [Zn(glu)]_n 2-D network. Adjacent [Zn(glu)]_n 2-D networks are bridged by bix ligands to construct a 6-connected 3-D network based on the Zn₂ unit. 2 shows an undulated 2-D (4,4) network. The interesting structural feature of 2 is that there are 1-D water chains. The O–H···O hydrogen bond interactions link the 2-D coordination networks and construct the 3-D supramolecular architecture in 2. The glu ligands are bis-(bidentate) bridges in 1 and bis-(monodentate) bridges in 2. The luminescence of 1 and thermal stability of 1 and 2 were investigated.     

Complexation behaviour of a CT complex composed of 9,10-bis(3,5-dihydroxyphenyl)anthracene and viologen derivatives

A chiral charge-transfer (CT) complex was formed using achiral 9,10-bis(3,5-dihydroxyphenyl)anthracene (BDHA) as an electron donor and achiral 1,1′-dimethyl-4,4′-bipyridinium dichloride (MVCl₂) as an electron acceptor. This chiral CT complex can include n-alkyl alcohol molecules as guests. On the other hand, when 1,1′-diphenyl-4,4′-bipyridinium dichloride and 1,1′-dibenzyl-4,4′-bipyridinium dichloride were used as electron acceptors, achiral CT complexes without guests were formed. It was found that the chiral crystallisation of the BDHA/MVCl₂–CT host system was caused by steric and electric intermolecular interactions between host component molecules BDHA and MVCl₂ during crystallisation.     

Syntheses and structures of three manganese coordination polymers with 1,4- bis (imidazol-1-yl)butane

Three manganese coordination polymers [Mn(bimb)₂(NCS)₂] _n (1), [Mn(bimb)₂(dca)₂] _n (2) and [Mn(bimb)₂(N₃)₂] _n (3) (bimb?=?1,4-bis(imidazol-1-yl)butane, dca?=?dicyanamide) were synthesized and characterized by X-ray crystallography, IR and thermogravimetric analysis. In 1 and 2, each Mn(II) links two Mn(II) atoms by double bimb ligands and extends to form a one-dimensional double chain structure containing the Mn₂(bimb)₂ 22-member metallocycle. 3 constructs a two-dimensional (4,4) network linked by bimb bridges.     

Construction of metal-organic frameworks through coordination and hydrogen bonding interactions: Syntheses, structures and photoluminescent properties of metal complexes with macrocyclic ligand

A macrocyclic ligand L with two diethylenetriamine units linked by two rigid biphenylene spacers was used as building block for construction of metal-organic frameworks. A silver(I) complex with macrocyclic and open-chain mix-type ligands [Ag₂(L)(L′)](ClO₄)₂ (1) [L′=1,6-bis(4-imidazol-1′-ylmethylphenyl)-2,5-diazahexane] was obtained by reaction of L and L′ together with AgClO₄·H₂O. It is interesting that the open-chain tetradentate ligand L′ only served as a bidentate ligand to bridge the Ag₂L units into an infinite one-dimensional (1D) cationic chain. Neutral 1D chain coordination polymer [Cu₂(L)(μ-SO₄)₂]·3H₂O·3MeOH (2) is formed by sulfate bridges between the neighboring Cu₂L units. When L reacted with nickel(II) sulfate instead of copper(II) sulfate, a monomacrocycle molecular complex [Ni₂(L)(H₂O)₄(SO₄)₂] (3) was obtained in which the sulfate anion acts as monodentate ligands rather than as bridges. When Cd(II) salts were used for the reactions with L, another two neutral 1D coordination polymers, [Cd₂(L)(μ-Cl)₂Cl₂]·2H₂O (4) and [Cd₂(L)(μ-Br)₂Br₂] (5), with the same structure were isolated. All the synthesized complexes exhibit three-dimensional framework structures linked by various hydrogen bonds. The photoluminescent properties of the synthesized complexes were studied in the solid state at room temperature, and the Ag(I) and Cd(II) complexes were found to show strong blue luminescence.     

Synthesis,characterization, and crystal structures of two coordination polymers from 3,5-bis(pyridin-4-ylmethyl) aminobenzoic acid

Aqueous medium reactions of transition metal salts with HL under hydrothermal conditions at 90°C led to two new coordination polymers, [M(L)₂(H₂O)₂]?·?H₂O [M?=?Co(1) and Mn(2); HL?=?3,5-bis(pyridin-4-ylmethyl)aminobenzoic acid]. HL contains both flexible N-donor groups [(pyridin-4-ylmethyl)amino] and carboxylate. The flexibility of (pyridin-4-ylmethyl)amino endows HL the ability to adopt varied conformations and coordination modes. Due to the presence of nitrogen and oxygen of HL and water in the reaction system, hydrogen-bonding interactions are available to assemble donor and acceptor building blocks. The two complexes are structurally similar to L^? doubly interconnecting M(II) to form 1-D chains. The extension of the 1-D chain through hydrogen-bonding forms fascinating 3-D supramolecular frameworks. FT-IR spectroscopy and thermal stability have been studied. The two compounds represent the first complexes containing 3,5-bis(pyridin-4-ylmethyl)amino benzoate.     

Synthesis and Crystal Structure of an Infinite 1D Zigzag Chain Compound (dimbH~+)(ClO_4~-) and Its Comparison with (dimb)2H_2O (dimb = 1,3-Di(imidazol-1-ylmethyl)-5-methylbenzene)

1 INTRODUCTION Recently the rational design and preparation of novel functional materials are one of the highlights in supramolecular chemistry and crystal engi- neering[1]. How to control the molecular structures and topology in the process of self-assembly has attracted extensively attention[2]. To date, a lot of complexes containing well-designed bidentate[3～6], tripodal[7, 8] and hexadentate[9] imidazole moiety ligands have been synthesized by chemists. Some of them have interestin…     

Syntheses,crystal structures and properties of two cadmium coordination polymers containing bis (2-methylimidazol-1-yl)methane(2-mBIM) and bis (imidazol-1-yl)methane (BIM) ligands

Coordination polymers, {[Cd(2-mBIM)₃](ClO₄)₂} _n (1) and [Cd(BIM)₂(NO₃)₂] _n (2), have been prepared from the reaction of bis(2-methylimidazol-1-yl)methane(2-mBIM) with Cd(ClO₄)₂ and bis(imidazol-1-yl)methane (BIM) with Cd(NO₃)₂ in ethanol and water, respectively. Their structures were characterized by single crystal X-ray diffraction and IR spectroscopy. Compound 1 crystallizes in the rhombohedral space group R-3c with a = b = 12.3617(5) Å, c = 38.896(3) Å, γ = 120°, V = 5147.5(5) ų, z = 6. The Cd^II occupies a crystallographic inversion center and is coordinated by six N atoms from six distinct 2-mBIM ligands to form a slightly distorted octahedral geometry. Each 2-mBIM is coordinated to two Cd^II cations, linking alternatively four Cd^II cations, resulting in a 32-membered M₄L₄ macrometallacycle. Compound 2 crystallizes in the monoclinic space group C2/m with a = 14.400(3) Å, b = 9.3894(18) Å, c = 8.6926(17) Å, β = 123.499(2)°, V = 980.1(3) ų, z = 2. The Cd coordinates to four nitrogen atoms from four different BIM and two nitrates to form a slightly distorted octahedral geometry. The BIM ligands bridge to form a 1-D infinite double-bridged chain structure with 16-membered M₂L₂ macrometallacyclic structural units.     

Syntheses and structures of two copper coordination polymers with bis (1,2,4-triazol-1-ylmethyl)benzene and benzenedicarboxylate

Two copper coordination polymers [Cu(obtz)(bdc)] _n (1) and {[Cu(obtz)(phth)] · 2H₂O} _n (2) (obtz = 1,2-bis(1,2,4-triazol-1-ylmethyl)benzene, bdc = 1,3-benzenedicarboxylate, phth = 1,4-benzenedicarboxylate) were synthesized and characterized. Both 1 and 2 are 2-D networks constructed via the bridging ligands bdc and phth. The obtz ligands do not extend the dimension (2-D network) but add their thickness, 10.9 Å for 1 and 11.6 Å for 2. Complex 1 further constructs a 3-D network via π?π stacking interactions between the benzene rings of obtz ligands of adjacent 2-D networks. The thermal stabilities have been investigated.     

两个二维层状4-双(咪唑基-1-甲基)-苯钴和镍配位聚合物的合成与表征

以1,4-双(咪唑基-1-甲基)-苯(bix)为配体,间苯二甲酸(IPA)为辅助配体,合成制备了两种新型同构配位聚合物:{[Ni(bix)(IPA)(H_2O)]}_n(1)和{[Co(bix)(IPA)(H_2O)]}_n(2)。单晶结构表明,此两个配合物均形成二维层状空间结构,金属原子均为六配位八面体结构,赤道平面上四个配位原子来自间苯二甲酸和配位水分子,轴向两个配位原子为bix配体的咪唑环上的N原子。金属原子通过配体连接形成四连接的二维4(4).6(2)方格层状结构。     

Syntheses and structures of three new coordination polymers with the flexible 1,4- bis (imidazol-1-yl)butane ligand

Three new coordination polymers [Co(bimb)₂(NCS)₂] _n (1), {[Co(bimb)₂(dca)₂]?·?CH₃CN} _n (2) and [Cu(bimb)₂(NO₃)₂] _n (3) (bimb?=?1,4-bis(imidazol-1-yl)butane, dca?=?dicyanamide) were synthesized and characterized. In 1, each Co(II) links two Co(II)'s by double bimb ligands and extends to form a one-dimensional chain containing the Co₂(bimb)₂ 22-membered metallocycle. 2 and 3 are two-dimensional (4, 4) networks linked by bimb bridges. The conformations of the bimb ligands in 1, 2 and 3 are analyzed.     

9,10-二(苯亚甲基-硫亚甲基)蒽的合成及其对Cu2+的识别

荧光分子开关和分子识别是超分子化学的重要组成部分。蒽环作为一个优良的荧光基团被广泛应用于分子开关的设计及分子识别中。Resorci-narenes母体衍生物的合成研究中采用蒽环作为荧光基团已被报道多次[1-4],Luigi Fabbrizzi合成的多氨基蒽衍生物[5]对Zn2 具有良好的PET效应。蒽系荧光分子在分子逻辑门系统中日益受到了研究者的重视,de Silva等在研究中发现一蒽环化合物[6]在Mg2 作用存在OR逻辑行为。在后续研究中发现两类蒽环化合物在一定条件下分别存在AND[7]和NOR[8]逻辑行为。在分子识别的研究中,Shin-ichi Sasaki合成的含穴状…     

一维链状配位聚合物[Co(imbz)_2(H_2O)_2]_n[imbz=4′-(1-咪唑基亚甲基)苯甲酸根]的合成及晶体结构(英文)

０ＩｎｔｒｏｄｕｃｔｉｏｎＮｕｍｅｒｏｕｓｕｎｉｑｕｅｆｒａｍｅｗｏｒｋｓｈａｖｅｂｅｅｎｒｅｐｏｒｔｅｄｂｙａｓｓｅｍｂｌｙｏｆｒａｔｉｏｎａｌｄｅｓｉｇｎｅｄｏｒｇａｎｉｃｌｉｇ-ａｎｄｓｗｉｔｈｍｅｔａｌｉｏｎｓｏｖｅｒｔｈｅｐａｓｔｄｅｃａｄｅ１～３．Ｉｔｉｓｋｎｏｗｎｔｈａｔｂｏｔｈｉｍｉｄａｚｏｌｅａｎｄｃａｒｂｏｘｙｌａｔｅａｒｅｆｕｎｃｔｉｏｎａｌｇｒｏｕｐｓｆｏｒｃｏｏｒｄｉｎａｔｉｏｎｔｏｔｒａｎｓｉｔｉｏｎｍｅｔａｌｉｏｎｓｔｏｆｏｒｍｃｏｍｐｌｅｘｅｓ４～６．Ｈｏｗｅｖｅ…     

金属离子导向的2,2'-联苯甲酸和1,4-二(1-苯并咪唑基甲基)苯构筑的配合物的合成、结构和性质

在溶剂热条件下合成并表征了2个基于2,2''-联苯甲酸（H₂dpa）和1,4-二（1-苯并咪唑基甲基）苯（bbix）的配位聚合物：[Cu₂（bbix）（dpa）₂（C₂H₅OH）₂]_n（1）,{[Cd（bbix）_0.5（dpa）]·0.5H₂O}_n（2）。两者均显示二维结构。1中含有Cu-dpa螺旋链,bbix进而将螺旋链连接形成以Cu（Ⅱ）离子为3-连节点的6³波浪状网格。而在配合物2中,dpa^2-与Cd（Ⅱ）形成四-元环和八-元环交替连接而成的带状一维链,并由bbix连接得到二维网格。此外,还研究了1和2的热稳定性以及室温下2的荧光性能。     

金属离子导向的2,2'-联苯甲酸和1,4-二(1-苯并咪唑基甲基)苯构筑的配合物的合成、结构和性质

在溶剂热条件下合成并表征了2个基于2,2''-联苯甲酸（H₂dpa）和1,4-二（1-苯并咪唑基甲基）苯（bbix）的配位聚合物：[Cu₂（bbix）（dpa）₂（C₂H₅OH）₂]_n（1）,{[Cd（bbix）_0.5（dpa）]·0.5H₂O}_n（2）。两者均显示二维结构。1中含有Cu-dpa螺旋链,bbix进而将螺旋链连接形成以Cu（Ⅱ）离子为3-连节点的6³波浪状网格。而在配合物2中,dpa^2-与Cd（Ⅱ）形成四元环和八元环交替连接而成的带状一维链,并由bbix连接得到二维网格。此外,还研究了1和2的热稳定性以及室温下2的荧光性能。     

Syntheses,Structures and Properties of Four Manganese Coordination Polymers Derived from 4-Amino-3,5-bis(imidazol-1-ylmethyl)-1,2,4-triazole

The reaction of 4‐amino‐3,5‐bis(imidazol‐1‐ylmethyl)‐1,2,4‐triazole (abit) and manganese(II) salts yields four coordination polymers {[Mn(abit)₃](ClO₄)₂}_n ( 1 ), {[Mn(abit)₃](PF₆)₂}_n ( 2 ), [Mn(abit)(dca)₂(H₂O)₂]_n ( 3a ) and [Mn(abit)(dca)₂(H₂O)₂]_n ( 3b ). Compounds 1 and 2 are one‐dimensional triple‐stranded chain. Compounds 3a and 3b are polymorphous and construct one‐dimensional single chain. The conformational analysis is performed. The thermal properties have been investigated.     

A mild,efficient and selective iodination of aromatic compounds using iodine and 1,4-bis(triphenylphosphonium)-2-butene peroxodisulfate

A simple and efficient method for the iodination of aromatic compounds has been achieved in the presence of iodine and 1,4-bis(triphenylphosphonium)-2-butene peroxodisulfate.     

Syntheses and crystal structures of two supramolecular isomers of manganese(II) with 3,5-bis(isonicotinamido)benzoate

Two new supramolecular isomeric complexes [Mn(BBA)₂(H₂O)₂] _n · 4nH₂O (1) and [Mn(BBA)₂(H₂O)₂] · 4H₂O (2) were obtained by hydrothermal reactions of MnCl₂ · 4H₂O with 3,5-bis(isonicotinamido)benzoic acid (HBBA) under different ratio of NaOH/HBBA. Complex 1 is a 1-D zigzag chain in which the Mn(II) is six-coordinate with distorted octahedral geometry. The 1-D chains are further connected by hydrogen bonds to give a 3-D supramolecular framework. Complex 2 is a monomeric molecular complex, assembled through intermolecular hydrogen bonds into a 3-D supramolecular network. Reaction conditions have remarkable influence on the structures of the complexes. The thermal and non-linear optical properties of the complexes were studied.