The Role of the Coordination Modes of a Flexible Bis(pyridylamide) Ligand in the Topology of 2D Copper(II) Complexes

2012 ◽  
Vol 67 (9) ◽  
pp. 877-886 ◽  
Author(s):  
Xiu-Li Wang ◽  
Peng Liu ◽  
Jian Luan ◽  
Hong-Yan Lin ◽  
Chuang Xu
Keyword(s):  
Self Assembly ◽  
Three Dimensional ◽  
Carbonyl Oxygen ◽  
Carbon Paste ◽  
X Ray Diffraction ◽  
Pyridyl Nitrogen ◽  
Benzenedicarboxylic Acid ◽  
Metal Organic ◽  
Coordination Layer

Two new two-dimensional copper(II) coordination polymers, [Cu(L)(BDC)]_H2O (1) and [Cu2(L)0:5(SIP)(OH)(H2O)] 2H2O (2) [L=N;N0-bis(3-pyridylamide)-1,6-hexane, H2BDC=1,3- benzenedicarboxylic acid, H3SIP=5-sulfoisophthalic acid (3,5-dicarboxybenzenesulfonic acid)], have been synthesized hydrothermally by self-assembly of the flexible bis-pyridyl-bis-amide ligand L and the aromatic polycarboxylate ligands H2BDC or H3SIP. X-Ray diffraction analysis reveals that complex 1 displays a metal-organic coordination layer with a binodal (3,5)-connected {42.67.8}{42.6} topology, in which the L ligands adopt a m2-bridging mode (via ligation of the pyridyl nitrogen atoms). Complex 2 also exhibits a layered network based on tetranuclear copper clusters [Cu4(μ3-OH)2(H2O)2(O2C-)4], L ligands and SIP anions, showing a binodal (4,8)-connected network with {414.610.84}{44.62} topology, in which the L ligands adopt a μ6-bridging coordination mode (via ligation of the pyridyl nitrogen and carbonyl oxygen atoms). Adjacent layers in 1 and 2 are further linked by hydrogen bonding interactions to form three-dimensional supramolecular frameworks. The electrochemical behavior of the two complexes in bulk-modified carbon paste electrodes has been investigated

Syntheses, Structures and Electrochemical Properties of Two New Copper(II) Complexes Based on Isomeric Bis(pyridylformyl)piperazine Ligands and Rigid=Flexible Organic Dicarboxylates

2013 ◽  
Vol 68 (2) ◽  
pp. 138-146 ◽  
Author(s):  
Hong-Yan Lin ◽  
Peng Liu ◽  
Xiu-Li Wang ◽  
Chuang Xu ◽  
Guo-Cheng Liu
Keyword(s):  
Electrochemical Properties ◽  
Self Assembly ◽  
Three Dimensional ◽  
Supramolecular Network ◽  
Stacking Interactions ◽  
X Ray Diffraction ◽  
Pyridyl Nitrogen ◽  
X Ray ◽  
Network Complex ◽  
Polymeric Framework

Two new copper(II) complexes, [Cu2(3-bpfp)(2,6-PDA)2(H2O)2] (1) and [Cu(4-bpfp)0:5 (glu)]·H2O (2), have been hydrothermally synthesized by self-assembly of isomeric bis(pyridylformyl)piperazine ligands [3-bpfp=bis(3-pyridylformyl)piperazine, 4-bpfp=bis(4- pyridylformyl)piperazine], rigid pyridine-2,6-dicarboxylic acid (2,6-H2PDA) or flexible glutaric acid (H2glu), and copper(II) chloride. Single-crystal X-ray diffraction analysis reveals that two adjacent CuII ions are connected by the 3-bpfp ligand to build a dinuclear unit in complex 1, in which 2,6-PDA serves as a terminal chelating ligand. Adjacent dinuclear units are further linked by hydrogen bonding and π-π stacking interactions to form a three-dimensional (3D) supramolecular network. Complex 2 is a 3D coordination polymeric framework based on a layer polymer [Cu(glu)]n and bridging 4-bpfp ligands with 6-connected (44.610.8) topology. In 1 and 2, the ligands 3-bpfp and 4-bpfp adopt a μ2-bridging coordination mode (via ligation of pyridyl nitrogen atoms). The thermal stability and the electrochemical properties of the title complexes have been studied.

A new three-dimensional manganese(II) coordination polymer based on the 1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene ligand

2016 ◽  
Vol 72 (11) ◽  
pp. 895-900
Author(s):  
Xin-Hua Lu ◽  
Kai-Long Zhong
Keyword(s):  
Coordination Polymer ◽  
Crystal Engineering ◽  
Self Assembly ◽  
Three Dimensional ◽  
Dimensional Structure ◽  
X Ray Diffraction ◽  
Ligand Coordination ◽  
Metal Organic ◽  
And Control ◽  
Methyl Benzene

The self-assembly of coordination polymers and the crystal engineering of metal–organic coordination frameworks have attracted great interest, but it is still a challenge to predict and control the compositions and structures of the complexes. Employing multidentate organic ligands and suitable metal ions to construct inorganic–organic hybrid materials through metal–ligand coordination and hydrogen-bonding interactions has become a major strategy. Recently, imidazole-containing multidentate ligands that contain an aromatic core have received much attention. A new three-dimensional MnIIcoordination polymer based on 1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene, namely poly[(ethane-1,2-diol-κO)(μ-sulfato-κ2O:O′){μ3-1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene-κ3N:N′:N′′}manganese(II)], [Mn(SO4)(C18H18N6)(C2H6O2)]n, was synthesized and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Crystal structural analysis shows that there are two kinds of crystallographically independent MnIIcentres, each lying on a centrosymmetric position and having a similar six-coordinated octahedral structure. One is coordinated by four N atoms from four 1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene (timb) ligands and two O atoms from two different bridging sulfate anions. The second is surrounded by two timb N atoms and four O atoms, two from sulfate anions and two from two ethane-1,2-diol ligands. The tripodal timb ligand bridges neighbouring MnIIcentres to generate a two-dimensional layered structure running parallel to theabplane. Adjacent layers are further bridged by sulfate anions, resulting in a three-dimensional structure with3,4,6-ctopology. Thermogravimetric analysis of the title polymer shows that it is stable up to 533 K. The first weight loss between 533 and 573 K corresponds to the release of coordinated ethane-1,2-diol molecules, and further decomposition occurred at 648 K.

Two new isomeric zinc(II) metal–organic frameworks based on 1,5-bis(2-methyl-1H-imidazol-1-yl)pentane and 5-methylisophthalate ligands

2017 ◽  
Vol 73 (2) ◽  
pp. 78-83
Author(s):  
Xiong-Wen Tan ◽  
Heng-Feng Li ◽  
Chang-Hong Li
Keyword(s):  
Self Assembly ◽  
Metal Organic Frameworks ◽  
Three Dimensional ◽  
Central Metal Atom ◽  
Central Metal ◽  
X Ray Diffraction ◽  
Hydrothermal Conditions ◽  
X Ray ◽  
Mixed Ligands ◽  
Metal Organic

Many factors, such as temperature, solvent, the central metal atom and the type of coligands, may affect the nature of metal–organic frameworks (MOFs) and the framework formation in the self-assembly process, which results in the complexity of these compounds and the uncertainty of their structures. Two new isomeric ZnIImetal–organic frameworks (MOFs) based on mixed ligands, namely, poly[[μ-1,5-bis(2-methyl-1H-imidazol-1-yl)pentane-κ2N3:N3′](μ-5-methylisophthalato-κ2O1:O3)zinc(II)], [Zn(C9H6O4)(C13H20N4)]n, (I), and poly[[μ-1,5-bis(2-methyl-1H-imidazol-1-yl)pentane-κ2N3:N3′](μ3-5-methylisophthalato-κ3O1:O1′:O3)(μ3-5-methylisophthalato-κ4O1:O1′:O3,O3′)dizinc(II)], [Zn2(C9H6O4)2(C13H20N4)]n, (II), have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and thermogravimetric analysis. Complex (I) displays a two-dimensional layer net, while complex (II) exhibits a twofold interpenetrating three-dimensional framework. Both complexes show high stability and good fluorescence in the solid state at room temperature.

A three-dimensional twofold interpenetrated cobalt(II) MOF containing a flexible carboxylate-based ligand: synthesis, structure and magnetic properties

2018 ◽  
Vol 74 (4) ◽  
pp. 418-423 ◽  
Author(s):  
Yan-Yan An ◽  
Li-Ping Lu ◽  
Miao-Li Zhu
Keyword(s):  
Self Assembly ◽  
Three Dimensional ◽  
Antiferromagnetic Coupling ◽  
X Ray Diffraction ◽  
Hydrothermal Conditions ◽  
X Ray ◽  
Design And Synthesis ◽  
Metal Organic ◽  
Cluster Representation ◽  
Methyl Benzene

The design and synthesis of coordination polymers (CPs) have attracted much interest due to the intriguing diversity of their architectures and topologies. The functional solid catena-poly[μ2-aqua-triaqua{μ4-5-[4-carboxyphenoxy)methyl]benzene-1,3-dicarboxylato}{μ3-5-[4-carboxyphenoxy)methyl]benzene-1,3-dicarboxylato}dicobalt(II)], [Co2(C16H10O7)2(H2O)4] n or [Co2(HL)2(μ2-H2O)(H2O)3] n , was synthesized successfully by self-assembly of CoII ions with 5-[(4-carboxyphenoxy)methyl]isophthalic acid (H3 L). The title compound was obtained under hydrothermal conditions and exhibits a twofold interpenetrated three-dimensional skeleton with hms 3,5-conn topology according to the cluster representation for valence-bonded metal–organic frameworks (MOFs). It has been characterized by single-crystal X-ray diffraction, IR spectroscopy, powder X-ray diffraction (PXRD), thermogravimetric analysis and susceptibility measurements. The antiferromagnetic coupling between adjacent CoII centres occurs via superexchange through the ligands.

Ligand Constraints and Synthesis of Metal–Organic Polyhedra

2015 ◽  
Vol 68 (5) ◽  
pp. 707 ◽  
Author(s):  
Harsh Vardhan ◽  
Francis Verpoort
Keyword(s):  
Metal Ions ◽  
Self Assembly ◽  
Three Dimensional ◽  
The Self ◽  
Bend Angle ◽  
Metal Organic ◽  
Discrete Structures ◽  
Hydrophobic Nature ◽  
Internal Volume

Metal–organic polyhedra are three dimensional discrete structures typically constructed by the self-assembly of metal ions and ligands. The synthesis and geometry of discrete structures entirely rely on the choice of metal ions, ligand constraints such as steric bulk, bend angle, and functionalities, and the nature of applied solvents. As a result, they provide tailorable internal volume and usually hydrophobic nature to the cavity that in turn makes them one of the prominent host molecules for a range of applications. This review highlights the intervention of ligand constraints, precisely bend angle (0°, 60°, 120°, and 180°), hydroxyl functionalities, and the role of concepts such as molecular panelling and subcomponent self-assembly in the synthesis of polyhedra.

Synthesis, crystal structure and photoluminescence of a three-dimensional zinc coordination compound with NBO-type topology

2019 ◽  
Vol 75 (3) ◽  
pp. 277-282 ◽  
Author(s):  
Xi Liu ◽  
Bo Fu ◽  
Lin Li ◽  
Yun-Fei Jian ◽  
Si Shu
Keyword(s):  
Crystal Engineering ◽  
Self Assembly ◽  
Materials Science ◽  
Three Dimensional ◽  
X Ray Diffraction ◽  
Paddle Wheel ◽  
Pyramidal Geometry ◽  
Carboxylate Groups ◽  
Potential Applications ◽  
Metal Organic

The assembly of metal–organic frameworks (MOFs) with metal ions and organic ligands is currently attracting considerable attention in crystal engineering and materials science due to their intriguing architectures and potential applications. A new three-dimensional MOF, namely poly[[diaqua(μ8-para-terphenyl-3,3′,5,5′-tetracarboxylato)dizinc(II)] dimethylformamide disolvate monohydrate], {[Zn2(C22H10O8)(H2O)2]·2C3H7NO·H2O} n , was synthesized by the self-assembly of Zn(NO3)2·6H2O and para-terphenyl-3,3′,5,5′-tetracarboxylic acid (H4TPTC) under solvothermal conditions. The compound was structurally characterized by FT–IR spectroscopy, elemental analysis and single-crystal X-ray diffraction analysis. Each ZnII ion is located in a square-pyramidal geometry and is coordinated by four carboxylate O atoms from four different TPTC4− ligands. Pairs of adjacent equivalent ZnII ions are bridged by four carboxylate groups, forming [Zn2(O2CR)4] (R = terphenyl) paddle-wheel units. One aqua ligand binds to each ZnII centre along the paddle-wheel axis. Each [Zn2(O2CR)4] paddle wheel is further linked to four terphenyl connectors to give a three-dimensional framework with NBO-type topology. The thermal stability and solid-state photoluminescence properties of the title compound have also been investigated.

Novel Ba2+ and Pb2+ metal–organic frameworks based on a semi-rigid tetracarboxylic acid: syntheses, structures, topologies and luminescence properties

2021 ◽  
Vol 77 (6) ◽  
Author(s):  
Yanwen Sun ◽  
Zhen Chen ◽  
Xiaozhong Wang ◽  
Lei Wang ◽  
Xue Yang ◽  
...  
Keyword(s):  
Self Assembly ◽  
Metal Organic Frameworks ◽  
Three Dimensional ◽  
Luminescence Properties ◽  
Tetracarboxylic Acid ◽  
X Ray Diffraction ◽  
X Ray ◽  
Secondary Building Units ◽  
Metal Organic ◽  
The Rich

Multidentate carboxylate ligands have been widely used in the construction of metal–organic frameworks (MOFs) owing to the rich variety of their coordination modes, which can lead to crystalline products with interesting structures and properties. Two new main-group MOFs, namely, poly[[di-μ-aqua-diaqua(dimethylformamide)[μ7-5,5′-methylenebis(2,4,6-trimethylbenzene-1,3-dicarboxylato)]dibarium(II)] trihydrate], {[Ba2(C23H20O8)(C3H7NO)(H2O)4]·3H2O} n or {[Ba2(BTMIPA)(DMF)(H2O)4]·3H2O} n (1), and poly[[diaqua[μ6-5,5′-methylenebis(2,4,6-trimethylbenzene-1,3-dicarboxylato)]dilead(II)] 2.5-hydrate], {[Pb2(C23H20O8)(H2O)2]·2.5H2O} n or {[Pb2(BTMIPA)(H2O)2]·2.5H2O} n (2), were prepared by the self-assembly of metal salts with the semi-rigid tetracarboxylic acid ligand 5,5′-methylenebis(2,4,6-trimethylisophthalic acid) (H4BTMIPA). Both structures were characterized by elemental analysis (EA), single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), IR spectroscopy and thermogravimetric analysis (TGA). Complex 1 reveals a three-dimensional (3D) flu network formed via bridging tetranuclear secondary building units (SBUs) and complex 2 displays a 3D framework with an sqp topology based on one-dimensional metal chains. The BTMIPA4− ligands adopt a rare coordination mode in 2, although the ligands in both 1 and 2 are X-shaped. The luminescence properties of both complexes were investigated in the solid state.

Synthesis and Characterization of Lanthanide Metal-Organic Frameworks with Perfluorinated Linkers

2016 ◽  
Vol 98 ◽  
pp. 70-74
Author(s):  
Andrius Laurikėnas ◽  
Jurgis Barkauskas ◽  
Aivaras Kareiva
Keyword(s):  
Metal Organic Frameworks ◽  
Aqueous Media ◽  
Xrd Analysis ◽  
X Ray Diffraction ◽  
Lanthanide Elements ◽  
Diffusion Controlled ◽  
Benzenedicarboxylic Acid ◽  
Metal Organic ◽  
Lanthanide Metal

In this study, lanthanide elements (Ln3+) and 2,3,5,6-tetrafluoro-1,4-benzenedicarboxylic acid (TFBDC) based metal-organic frameworks (MOFs) were synthesized by precipitation and diffusion-controlled precipitation methods. Powders insoluble in aqueous media and polar solvents were obtained. The microstructure and properties of Ln3+ MOFs were evaluated and discussed. X-ray diffraction (XRD) analysis, infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and fluorescence spectroscopy (FLS) were carried out to characterize Ln3+ MOF's crystallinity, the microstructure, chemical composition and optical properties.

A New POM-Based Supramolecular Compound: Synthesis, Structure and Adsorptive Property of [Cu(phen)2]3[W6O19]

2014 ◽  
Vol 919-921 ◽  
pp. 2013-2016 ◽  
Author(s):  
Ya Bing Liu ◽  
Hong Jie Wang ◽  
Hong Kai Zhao
Keyword(s):  
Three Dimensional ◽  
Building Blocks ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Hybrid Compound ◽  
Adsorptive Property ◽  
X Ray ◽  
Hydrogen Bonding Interactions ◽  
Compound Synthesis ◽  
Metal Organic

A POM - based organice - inorganic hybrid compound with the chemical formula of[Cu (phen)2]3[W6O19] (phen = 1,10-phenanthroline) (1) has been hydrothermally synthesized andstructurally characterized by the elemental analysis, and single crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic space groupC2/c witha=18.319(4) Å,b= 17.311(4) Å,c= 22.248(4) Å,β= 112.40(3) o,V= 6523(2) Å3,Z= 4, R1= 0.0448, andwR2=0.1218. Compound 1 consists of the [W6O19]3-building blocks and [Cu (phen)2]+metal organic cationic moieties, which are packed together via the extensive hydrogen-bonding interactions to form a three-dimensional supramolecular framework. The adsorption of methylene blue (MB) under UV irradiation with 1 as the heterogeneous adsorbent has been investigated, showing a good adsorptive property of 1 for MB degradation.

scholarly journals Synthesis, Crystal Structure, and Properties of a New Coordination Polymer Built from N/O-Donor Mixed Ligands

Crystals ◽  
2018 ◽  
Vol 8 (10) ◽  
pp. 372
Author(s):  
Mei-An Zhu ◽  
Shuai-Shuai Han ◽  
Feng Deng ◽  
Jia-Le Li ◽  
Shui-Sheng Chen
Keyword(s):  
Coordination Polymer ◽  
Weak Interactions ◽  
Three Dimensional ◽  
Luminescent Properties ◽  
Tridentate Ligand ◽  
Supramolecular Polymer ◽  
X Ray Diffraction ◽  
X Ray ◽  
Mixed Ligands ◽  
Benzenedicarboxylic Acid

The coordination polymer, namely, [Cd(H2L)(nobda)]n (1) was prepared by the reaction of Cd(NO3)2·4H2O with 4-amino-1,2-benzenedicarboxylic acid (H2nobda) and 1,4-di(1H-imidazol-4-yl)benzene (H2L), and characterized by single-crystal X-ray diffraction, elemental analysis, infrared (IR) spectroscopy, thermogravimetric analysis, and powder X-ray diffraction (PXRD). The carboxylic acid of H2nobda ligands was completely deprotonated to be nobda2− anions, which act as tridentate ligand to connect the Cd2+ to form two-dimensional (2D) network, while the neutral H2L ligands serve as a linear didentate bridge to connect two adjacent Cd2+ ions upper and down the 2D layer. The adjacent 2D layers were further linked into the three-dimensional (3D) supramolecular polymer by the weak interactions such as hydrogen bonds and π−π stacking interactions. The ultraviolet-visible (UV-vis) absorption spectra and luminescent properties in the solid state at room temperature have been investigated.

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