A two‐dimensional zinc(II) coordination polymer created via in situ ligand synthesis involving C—N bond formation

The novel Zn^II coordination polymer poly[{μ₄‐2‐[3‐(pyridin‐2‐yl)‐1H‐pyrazol‐3‐yl]butanedioato}zinc(II)], [Zn(C₁₂H₉N₃O₄)]_n, has been synthesized hydrothermally and structurally characterized. The results demonstrate that the complex shows two‐dimensional neutral wave‐like layers. The complex was prepared by the conjugate addition reaction of 2‐(1H‐pyrazol‐3‐yl)pyridine to cis‐fumaric acid in the presence of Zn(OAc)₂·2H₂O (OAc is acetate) at 413 K.     

Syntheses and characterization of a new nano-structured bismuth(III) bromide coordination polymer; new precursor for preparation of bismuth(III) bromide and bismuth(III) oxide nanostructures

Nanoparticles of a Bi(III) coordination polymer, {[Bi(μ-4,4′-bipy)Br₄] · (4,4′-Hbipy)} _n (1) (4,4′-bipy = 4,4′-bipyridine), were synthesized by a sonochemical method. The new nanoparticles were characterized by scanning electron microscopy, X-ray powder diffraction (XRD), IR spectroscopy, and elemental analyses. Compound 1 was structurally characterized by single-crystal X-ray diffraction. The thermal stabilities of 1 as bulk and at nanosize were studied by thermal gravimetric (TG) and differential thermal analyses (DTA). The Bi₂O₃ and BiBr₃ nanostructures were obtained by calcinations of nanostructure of 1 in air and argon.     

Controlled assembly of zero-, one- and two-dimensional metal-organic frameworks involving in situ ligand synthesis under different reaction pH

Five cadmium(II) metal-organic frameworks, namely [Cd(BIPA)(daf)(H₂O)₃] · 2H₂O (1), Cd₂(BDC)₂(pdon)₂(H₂O)₂ (2), Cd(BIPA)(pdon) (3), Cd(BIPA)(daf) (4) and [Cd₂(BIPA)₂(pdon)₂] · H₂O (5) (H₂BIPA = 5-bromoisophthalic acid, H₂BDC = terephthalic acid, pdon = 1,10-phenanthroline-5,6-dione, daf = 4,5-diaza-fluoren-9-one), have been constructed from cadmium(II) salts with multi-carboxylate ligands and pdon ligands under different reaction pH. The framework structures of these polymeric complexes have been determined by the X-ray single crystal diffraction technique. The differences of the five metal-organic frameworks demonstrate that the reaction pH has an important effect on the structure of these complexes. The thermal analyses of these five complexes have been measured and discussed. Additionally, four complexes show strong fluorescence in the solid state at room temperature.     

A two‐dimensional zinc(II) coordination polymer based on mixed dimethyl succinate and bipyridine ligands: synthesis,structure, thermostability and luminescence properties

From the viewpoint of crystal engineering, the construction of crystalline polymeric materials requires a rational choice of organic bridging ligands for the self‐assembly process. Multicarboxylate ligands are of particular interest due to their strong coordination activity towards metal ions, as well as their various coordination modes and versatile conformations. The structural chemistry of dicarboxylate‐based coordination polymers of transition metals has been developed through the grafting of N‐containing organic linkers into carboxylate‐bridged transition metal networks. A new luminescent two‐dimensional zinc(II) coordination polymer containing bridging 2,2‐dimethylsuccinate and 4,4′‐bipyridine ligands, namely poly[[aqua(μ₂‐4,4′‐bipyridine‐κ²N:N′)bis(μ₃‐2,2‐dimethylbutanedioato)‐κ⁴O¹,O^1′:O⁴:O^4′;κ⁵O¹:O¹,O⁴:O⁴,O^4′‐dizinc(II)] dihydrate], {[Zn₂(C₆H₈O₄)₂(C₁₀H₈N₂)(H₂O)]·2H₂O}_n, has been synthesized under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction and elemental, IR and thermogravimetric analyses. In the structure, the 2,2‐dimethylsuccinate ligands link linear tetranuclear Zn^II subunits into one‐dimensional chains along the c axis. 4,4′‐Bipyridine acts as a tethering ligand expanding these one‐dimensional chains into a two‐dimensional layered structure. Hydrogen‐bonding interactions between the water molecules (both coordinated and free) and carboxylate O atoms strengthen the packing of the layers. Furthermore, the luminescence properties of the complex were investigated. The compound exhibits a blue photoluminescence in the solid state at room temperature and may be a good candidate for potential hybrid inorganic–organic photoactive materials.     

Spectroscopic and structural studies of the 2D Mn(II) coordination polymer from a bridging Noxa, Npy bidentate ligand; tetra-n-butylammonium[5-(3-pyridyl)-1,3,4-oxadiazole-2-thiolate]

A coordination polymer {[Mn(3-pyt)₂(H₂O)₂][N(n-Bu)₄]⁺[3-pyt]⁻}_n (3) has been synthesized from the reaction of tetra-n-butylammonium[5-(3-pyridyl)-1,3,4-oxadiazole-2-thiolate] {[N(n-Bu)₄]⁺[3-pyt]⁻} and Mn(OAc)₂ · 4H₂O. The ligand and the Mn(II) complex 3 have been characterized by elemental analyses, IR, ¹H and ¹³C NMR spectroscopy, in addition 3 has also been studied crystallographically. The single crystal X-ray structure of the 3 shows that the ligand is bonded to Mn(II) via its pyridyl and oxadiazole nitrogen atoms. This bonding pattern connects the Mn(II) centres to afford an uniform two dimensional coordination frame work where the [Mn(3-pyt)₂(H₂O)₂]_n molecules are stacked in a parallel layers. The overall arrangement of molecules in crystal lattice results in open channels in which the enclosed tetra-n-butylammonium cations are stabilized by anionic oxadiazole molecules through N⁺···S⁻ ionic interactions.     

Crystallographic report: A three‐dimensional zinc trimesate framework: [(CH3)2NH2][Zn(C9H3O6)]·(C3H7NO)

The structure features an anionic three‐dimensional network built from zinc ions and trimesate ligands. The structure contains parallelogrammic channels in which H₂NMe₂ molecules interact with dimethylformamide guest molecules and the framework through hydrogen bonds. Copyright © 2005 John Wiley & Sons, Ltd.     

New 1,2-dithioether based 2D copper(I) coordination polymer: from synthesis to catalytic application in A3-coupling reaction

Abstract

A new 2D copper(I) coordination polymeric complex has been synthesized from CuI and 1-(1-{4-chlorophenylthio}propan-2-ylthio)-4-chlorobenzene ([(CuI)₂{ArSCH₂CH(CH₃)SAr}₂]_n, Ar = 4-ClC₆H₄) and characterized by high resolution mass spectrometry (HRMS) and single crystal X-ray diffraction techniques. The complex has been employed as a suitable catalyst for a solvent-free, one-pot, three-component A³-coupling reaction. A variety of aromatic and aliphatic aldehydes, terminal alkynes and aliphatic cyclic secondary amines have been used to prepare a library of propargylamines using the 2D-Cu complex at significantly low concentration (0.2?mol%).     

Novel Zn（Ⅱ） ladder-like coordination polymer constructed from designed ferrocenyl ligand

Reaction of Zn（NO3）2·6H2O with 3-（4-carboxylphenylamino）-l-ferrocenyl-2-butylen-l-one （HL） and 4,4′-bipyfidine （4,4′- bipy） in methanol solution resulted in a novel ladder-like coordination polymer {[Zn2L2（μ2-L）2（4,4′-bipy）2]·MeOH}n （1）. Its crystal structure, thermal and electrochemical properties are presented.     

Thermal decomposition of potassium bis -oxalatodiaqua-indate(III) monohydrate

Indium (III) is precipitated with oxalic acid in the presence of potassium nitrate maintaining an overall concentration of 0·125 M in HNO₃. Chemical analysis of the complex salt obtained indicates the formula, K[In(C₂O₄)₂]·3H₂O. Thermal decomposition studies show that the compound decomposes first to the anhydrous potassium indium oxalate and then to the final mixture of the oxides through formation of potassium carbonate and indium (III) oxide as intermediates. Isothermal study, X-ray diffraction pattern and IR spectral data support the proposed thermal decomposition mechanism.     

One‐dimensional Europium(III) Coordination Polymer Based on 3‐Pyridylacrylic Acid

Under hydrothermal conditions, the reaction of racemic 3‐pyridyl‐3‐aminopropionic acid (rac‐HPAPA) with Eu(ClO₄)₃· 6H₂O affords a 1‐D chain complex, [Eu(3‐PYA)₃(H₂O)]_n ( 1 ) (3‐PYA=3‐pyridylacrylate), which represents an example of neutral 1‐D coordination polymeric material based on 3‐HPYA (HPYA= pyridylacrylic acid) ligand with strong red fluorescent emission in the solid state.     

Ultrasonic-assisted synthesis of two new nano-structured 3D lead(II) coordination polymers: Precursors for preparation of PbO nano-structures

Nano-structures of two new Pb(II) three-dimensional coordination polymers, [Pb₂(4-pyc)₂I₂(H₂O)]_n (1), {4-Hpyc = 4-pyridinecarboxilic acid} and [Pb(3-pyc)I]_n (2), {3-Hpyc = 3-pyridinecarboxilic acid} were synthesized by sonochemical method. The new nano-structures were characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. Compounds 1 and 2 were structurally characterized by single crystal X-ray diffraction and are three-dimensional coordination polymers. The thermal stability of compounds 1 and 2 both their bulk and nano-size were studied by thermal gravimetric and differential thermal analyses and compared. PbO block-structures were obtained by calcination of the nano-structures of compounds 1 and 2 at 400 °C.     

A 2D coordination polymer with 4*82 topology constructed from a new T -shaped ligand: synthesis,crystal structure and photoluminescence

A cadmium(II) coordination polymer [CdL(H₂O)] (1) (H₂L?=?3,3-bis(carboxymethyl)imidazo[1,2-a]pyridin-2-one) was synthesized under hydrothermal conditions and characterized by X-ray structure analysis. Compound 1 crystallizes in the monoclinic space group P2₁/n with a?=?11.945(2)?Å, b?=?8.0865(16)?Å, c?=?13.114(3)?Å, β?=?91.36(3)°, Z?=?4, and represents a 2D network with the 4*8² topology constructed from combination of metal centers with a T-shaped geometry and ligands with T-shaped structure simultaneously. Compound 1 also exhibits strong photoluminescence at room temperature.     

A square‐planar hydrated cationic tetrakis(methimazole)gold(III) complex

The cationic pseudo‐square‐planar complex tetrakis(1‐methyl‐2,3‐dihydro‐1H‐imidazole‐2‐thione‐κS)gold(III) trichloride sesquihydrate, [Au(C₄H₆N₂S)₄]Cl₃·1.5H₂O, was isolated as dark‐red crystals from the reaction of chloroauric acid trihydrate (HAuCl₄·3H₂O) with four equivalents of methimazole in methanol. The Au^III atoms reside at the corners of the unit cell on an inversion center and are bound by the S atoms of four methimazole ligands in a planar arrangement, with S—Au—S bond angles of approximately 90°.     

A manganese(II) coordination polymer with a 3D porous structure: Synthesis,structure, and spectroscopic and magnetic behaviour

A manganese(II) complex with N,N′-bis(carboxymethyl)dithiooxamide (H₄GLYDTO), [Mn(H₂GLYDTO)(H₂O)₂]_n, has been synthesized and characterized by elemental analysis and thermogravimetric analysis, as well as by infrared, electronic and EPR spectroscopy and magnetic susceptibility measurements. The crystal and molecular structure of this complex was determined by single-crystal X-ray structure analysis. The compound shows a 3D porous framework with alternate left- and right-handed helical channels where the manganese(II) ions have an octahedral environment. Variable temperature magnetic measurements reveal the existence of very weak antiferromagnetic interactions through the syn-anti carboxylate bridge, with an exchange parameter of J/k = −0.12 K.     

Synthesis, crystal structure and luminescent properties of a new 3D coordination polymer constructed by Cd(II) with 4,4′-oxybis(benzoate) and 4,4′-bipyridine

A new Cd(II) coordination polymer, [Cd(bpy)(oba)] _n (1) (H₂oba = 4,4′-oxybis(benzoic acid); bpy = 4,4′-bipyridine) has been synthesized under the hydrothermal conditions and structurally characterized by elemental analysis, IR spectrum and single crystal X-ray diffraction. X-ray diffraction analysis reveals that 1 features an interesting 3D framework with wavelike [Cd₂(oba)₂] _n ribbons linked by 4,4′-bpy bridges. The oba ligand adopts chelating and chelating/bridging coordination modes. 1 displays strong fluorescent emission in the solid state at room temperature. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Sonochemical synthesis and structural characterization of a nano-structure Pb(II) benzentricarboxylate coordination polymer: new precursor to pure phase nanoparticles of Pb(II) oxide

Microcrystals of a new Pb(II) coordination polymer, [Pb₂(1,3,5-HBTC)₂(H₂O)₄] · H₂O (1) (1,3,5-H₃BTC = 1,3,5-benzentricarboxylic acid), was synthesized by a sonochemical method. The structure was characterized by scanning electron microscopy, X-ray powder diffraction, elemental analyses, and IR spectroscopy. Thermal stability was studied by thermal gravimetric and differential thermal analyses. After the calcination of nanosized 1 at 400°C, pure phase nanosized Pb(II) oxide has been produced.