Synthesis and Crystal Structure of 1,4-Bis(2-hydroxymethylphenyl)-1,4-dioxabutane

1 INTRODUCTION Macrocyclic ligands and their metal complexes have received much attention due to their applications in ion transport, ion separation and as models in biomimic researches[1~7]. The synthetic methods of macrocyclic ligands and their metal complexes are mainly divided into three kinds[8]. The first one is synthesizing free ligand, then forming the metal complexes; the second is template synthesis; and the third is synthesizing the end-off or side-off precursor ligand, then c…     

Two Tetranuclear Zinc(Ⅱ) Coordination Polymers Based on 3,5-Bis(2-carboxylphenoxy)benzoic Acid with Highly Selective Sensing of Nitrobenzene

Two novel zinc(Ⅱ) coordination polymers, [Zn_2(BCB)(CH_3OH)(μ_3-OH)]n(1) and {[Zn_2(BCB)(μ_3-OH)(H_2O)_2]·CH_3OH}n (2), have been constructed from 3,5-bis(2-carboxylphenoxy)benzoic acid(H_3BCB) and characterized by elemental analysis(EA), IR, powder X-ray diffraction(PXRD), and thermogravimetric(TG) analyses. Structural analysis reveals that complexes 1 and 2 are both 1D polymeric chains with unprecedented tetranuclear {Zn_4(COO)_4(μ_3-OH)_2} clusters, which were further expanded into a 2D structure. Fluorescence measurements show that 1 and 2 have highly selective and sensitive detection of nitrobenzene.     

A New 2D Zinc(Ⅱ)Coordination Polymer Constructed by Imidazole-4,5-dicarboxylic Acid(H3IDC)and 1,4-Bis(imidazol-l-ylmethyl)-benzene(bix)

T A new 2D Zn(Ⅱ)coordination polymer[Zn(HIDC)(bix)0.5]n(1)was obtained by the hydrothermal reaction of ZnCI2,imidazole-4,5-dicarboxylic acid(H3IDC)and 1,4-bis(imidazol-1-ylmethyl)-benzene(bix)with a 2:2:1 mole ratio.X-ray diffraction crystal structural analysis reveals it crystallizes in monoclinic,space group P21/n with α=12.125(3),b=10.541(3),c=684,μ(MoKα)=1.730 mm-1,the final R=0.0439 and wR=0.0888 for 2101 observed reflections with Ⅰ＞2σ(Ⅰ).In 1,each zinc(Ⅱ)ion is five-coordinated with a slightly distorted trigonal bipyramidal coordination geometry,and each μ2-HIDC2-acts as a bridge to bond two neighboring Zn(Ⅱ)ions,leading to a 1D zigzag chain architecture.The adjacent zigzag chains are further linked by μ2-bix to form an infinite 2D network structure.The fluorescence spectrum of 1 exhibits intense emission at 466 nm when excited at 397 nm in solid state at room temperature.     

Two New Zn(Ⅱ) and Co(Ⅱ) Coordination Polymers Constructed by 4-Bromobenzoic Acid and 1,4-Bis(imidazol-1-yl)-butane: Synthesis,Crystal Structure and Theoretical Calculations

Two new coordination polymers, [Zn(bba)_2(bib)]_(2n)(1) and [Co_(0.5)(bba)(bib)_(0.5)]_(2n)(2)(Hbba = 4-bromobenzoic acid, bib = 1,4-bis(imidazol-1-yl)-butane), have been hydrothermally designed and synthesized, and their structures were determined by elemental analyses, IR spectroscopy, TG, fluorescence spectroscopy, X-ray single-crystal and powder diffraction. Complexes 1 and 2 both belong to the monoclinic system and exhibit one-dimensional zigzag chain-like structure. In addition, we analyzed Natural Bond Orbital(NBO) in using the PBE0/LANL2 DZ method built in Gaussian 03 Program. The calculation results indicated the obvious covalent interaction between the coordinated atoms and Zn(Ⅱ), Co(Ⅱ) ions.     

Hydrothermal Syntheses,Crystal Structures and Characteristics of Two New Isostructural Ni(Ⅱ) Coordination Polymers

Two new isostructure nickel(Ⅱ) coordination polymers, [Ni_2(5-Me-ip)(1,2-Bie)(H_2O)_2]_n(1) and [Ni2(5-Br-ip)(1,2-Bie)(H_2O)_2]n(2)(5-Me-H2 ip = 5-methylisophthalic acid, 5-Br-H2 ip = 5-mromoisophthalic acid, 1,2-Bie = 1,2-bis(imidazole)ethane), have been synthesized and structurally characterized by single-crystal X-ray diffraction. The result shows that complexes 1 and 2 crystallize in orthorhombic system, space group Pna21 with a = 16.3602(13), b = 10.1465(8), c = 21.8803(17) ?, V = 3632.1(5) ?3, Z = 4, D3 c = 1.525 g/cm, F(000) = 1728, R = 0.0292 and wR = 0.0668 for 6646 observed reflections(I 2σ(I)) for complex 1 and a = 16.409(3), b = 10.1625(17), c = 21.918(4) ?, V = 3654.9(11) ?3, Z = 4, Dc = 1.752 g/cm~3, F(000) = 1936, R = 0.0309 and wR = 0.0600 for 6809 observed reflections(I 2σ(I)) for complex 2. They both feature zigzag 2D layer structures, which are further staked along the a-axis through π···π and hydrogen interactions to form 3D supramolecular structures.     

A New 2D Zinc(Ⅱ) Coordination Polymer Constructed by Imidazole-4,5-dicarboxylic Acid(H_3IDC) and 1,4-Bis(imidazol-1-ylmethyl)-benzene(bix)

A new 2D Zn(Ⅱ) coordination polymer [Zn(HIDC)(bix)0.5]n(1) was obtained by the hydrothermal reaction of ZnCl2,imidazole-4,5-dicarboxylic acid(H3IDC) and 1,4-bis(imidazol-1-ylmethyl)-benzene(bix) with a 2:2:1 mole ratio.X-ray diffraction crystal structural analysis reveals it crystallizes in monoclinic,space group P21/n with a = 12.125(3),b = 10.541(3),c = 12.484(3) ,β = 115.834(4)°,V = 1436.0(6) 3,Mr = 338.60,Z = 4,Dc = 1.566 Mg·m-3,F(000) = 684,μ(MoKα) = 1.730 mm-1,the final R = 0.0439 and wR = 0.0888 for 2101 observed reflections with I ≥ 2σ(I).In 1,each zinc(Ⅱ) ion is five-coordinated with a slightly distorted trigonal bipy-ramidal coordination geometry,and each μ2-HIDC2-acts as a bridge to bond two neighboring Zn(Ⅱ) ions,leading to a 1D zigzag chain architecture.The adjacent zigzag chains are further linked by μ2-bix to form an infinite 2D network structure.The fluorescence spectrum of 1 exhibits intense emission at 466 nm when excited at 397 nm in solid state at room temperature.     

Synthesis,Structure and Fluorescence of Olefin-Copper(Ⅰ) Coordination Polymers

The organic olefin ligand 2,5-dimethyl-1-(4-vinyl-benzyl)-piperazine reacts with CuX(X = Cl, Br) to obtain two novel olefin-copper(I) coordination polymers [C_(15)H_(22)N_2Cu_2Cl_3]n(1) and [C_(15)H_(20)N_2Cu_2Br_2]n(2). There are two types of CuX warp structures that have never been seen before in the presence of methanol under solvothermal conditions. The new olefin-copper(I) coordination complex crystallizes in the monoclinic space group P21/c to obtain compounds 1 and 2. Its unique green fluorescence effect can be applied to the LED field.     

Two Novel 3D Wells–Dawson Based Coordination Polymers with Unusual Topological Structure Extended by 1,4-Bis(1,2,4-triazol-1-yl)butane

Two novel Wells–Dawson based coordination polymers, [Co₂(btb)₄(H₂O)][H₂X₂W₁₈O₆₂]·nH₂O (X = P for 1 and As for 2; n = 3 for 1 and 6 for 2) (btb = 1,4-bis(1,2,4-triazol-1-y1)butane), have been successfully isolated under hydrothermal conditions. Single crystal X-ray diffraction analyses reveal that isostructural compounds 1 and 2 exhibit 2D metal–organic layers, which are further linked by four-dentate [X₂W₁₈O₆₂]^6? anions to form an unusual (4,4,6)-connected self-penetrating 3D framework with the Schläfli symbol of {3·5·6⁴}{3²·5²·6⁶·7³·8²}{5²·6⁴}. To the best of our knowledge, this kind of topological structure has not been reported yet. The electrochemical and photocatalytic properties of compounds 1 and 2 have been investigated.     

Syntheses,Crystal Structures and Fluorescence of Cadmium(II) Coordination Polymers with Pyrazine-1,4-dioxide, 2-Methylpyrazine-1,4-dioxide and Thiocyanate as Mixed Bridge Ligands

1 INTRODUCTION For a long time much research interest has been focused on the coordination polymeric compounds because such new coordination polymers may afford new materials with useful properties, such as catalytic activity, micro-porosity, electrical conduc- tivity, non-linear optical activity, magnetic coupling behavior and so on[1, 2]. Thiocyanate anion as well as pyrazine-1,4-dioxide and its derivatives belongs to very useful bridge ligands and many complexes[3, 4] with one of them e…     

Two New Zn(Ⅱ)/Cd(Ⅱ) One-dimensional Coordination Polymers Based on Naphthalimide Dicarboxylic Ligand

The assemble reactions of 5-(1,3-dioxo-~1H-benzo[de]isoquinolin-2(3 H)-yl)isophthalic acid(H_2L) and Zn2+/Cd2+ ions led to two compounds: [ZnL(DMSO)2]?3DMSO(1) and [Cd2 L2(DMSO)4]?DMF(2). 1 and 2 feature 1 D coordination chains. Weak ?-? interactions further connect the 1 D chains into 2D supramolecular networks. Upon grinding, 1 and 2 show increase of quantum efficiencies(34.8 and 45.4 times of increase compared with original samples for the two compounds respectively) and red shift of the emission peaks(45 and 41 nm of shift compared with original samples for the two compounds, respectively). Both indicate the compounds are good mechanoluminescence responsive materials.     

Syntheses, Structures and Photoluminescence of Two New Europium（III） Coordination Polymers

Two new europium (Ⅲ) coordination polymers formulated as Eu2(H2O)2(ox)4 ]· (C5H6N)2 ·2H 2 O(1) and Eu 2(ad)3(H2O)4 ]·0.25H2O (2) (H2ox = oxalic acid, H2ad = adipic acid) have been synthesized from the self-assembly of lanthanide ions Eu 3+ with flexible oxalic and adipic acid ligands, respectively. Structural analyses revealed that complex 1 exhibits three-dimensional metalorganic frameworks, and 2 has intricate two-dimensional interpenetrated metal-organic networks. In addition, the photoluminescent properties of complexes 1 and 2 were discussed in detail, which shows strong red emission, corresponding to 5 D0 → 7 F 2 transition of Eu3+ ions.     

Coordination compounds of some metals with N,N′-Bis(m-ethoxycarbonylphenyl)urea

N,N′-bis(m-ethoxycarbonylphenyl)urea and its complex compounds with cooper, zinc and cadmium were syntesized. The structure of N,N′-bis(m-ethoxycarbonylphenyl)urea was investigated by XRD method. Ligand coordination process was determined. Some factors affecting the donor ability of the nitrogen and oxygen atoms in ligand molecule were discussed.     

Phase Transfer Catalyzed Synthesis of Diaryl 1,4—Phenylene Dioxydiacetate

The title compounds 3a—3o were prepared with high yield via the reaction of 1, 4-phenylenedioxydiacetyl chloride with various substituted phenols under the condition of liquid-liquid phase transfer catalysis, using polyethylene glycol—400 as the catalyst.     

Synthesis,Crystal Structure and Luminescence of One-dimensional Homochiral Terbium (Ⅲ) Coordination Polymers

Enantiomerically pure lanthanide(Ⅲ)-based phosphonates are successfully synthesized by using(R)-or(S)-(1-phenylethylamino)-methylphosphonate acid(pempH_2), namely, R-or S-[Tb_3(pempH_2)_2(pempH)_7]-Cl_2·H_2O(R-Tb or S-Tb), crystallizing in chiral space group P2_12_12_1. Compound R-Tb shows a one-dimensional homochiral triple-stranded helical chain structure where the Tb(III) atoms are bridged by O-P-O units and μ_3-O(P) bridge. The thermal analysis, photoluminescence as well as optically active properties of compounds R-Tb and S-Tb have also been investigated.     

Tuning the Photoluminescence of Zn(Ⅱ) Coordination Polymers by Changing the Coordinated Solvent

By using solvothermal method,two new Zn(Ⅱ) coordination polymers based on 2,5-furandicarboxylic acid(H_2FDA) ligand,[Zn(FDA)(CH_3OH)]_n(1) and [Zn_2(FDA)_2(CH_3CH_2OH)_2]_n(2),were synthesized and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR.Complexes 1 and 2 are isostructural coordination polymers with two-dimensional sheet structures bridged by the protonated carboxylates ligands.The 2D network can be rationalized as a 3-c net with Schl?fli symbol is 82·10.Although 1 and 2 are isostructural,the photoluminescent intensity of 2 is almost twice that of 1 due to the difference of coordinated solvents.     

Influence of Different Organic Carboxylate Anions on the Crystal Structure of Silver(Ⅰ)Coordination Polymers

The reaction of AgNO3 , 4,4′-bipyridine (bpy) and 2,2′-bipyridine-3,3′-dicarboxylic acid (H2bpdc)/2,2′-biquinoline-4,4′-dicarboxylic acid (H2bqdc)/1,3-benzenedicarboxylic acid (H2bdc) gave rise to block-like crystals of [Ag4(bpy)2(bpdc)2]·13H2O(1), [Ag2(bpy)(bqdc)(H2O)]·4.5H2O(2) and [Ag2(bpy)2(H2O)2](bdc)·3H2O(3) by slow evaporation. All the three complexes contain sandwich-like crystal structures, in which anionic sheets built up from different anions (bpdc2- , bqdc2- and bdc2- ) and lattice water molecules via rich hydrogen-bonding interactions are inserted between the cationic silver complex layers, and the abundant Ag···Ag, Ag···N and π-π stacking interactions further strengthen the 3D frameworks. The lattice water molecules are situated among the framework of crystal structure and stabilized by rich hydrogen-bonding interactions, and lattice water molecules may play a role in the orientation of organic anions in the crystal packing. Additionally, the thermal properties of 1, 2 and 3 were also discussed in detail.     

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

Two new supramolecular polymers [M(2-NH_2py)_2(ox)][M=Co(1),Ni(2);2-NH_2py=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-NH_2py)_2]2 units bridged by tetradentate oxalate ligands to form three-dimensional supramolecular network via the C-H…O hydrogen bonds and π-π stacking interactions.Compound 1 displays antiferromagnetic interaction.