Coordination polymers with pyridine-2,4,6-tricarboxylic acid and alkaline-earth/lanthanide/transition metals: synthesis and X-ray structures

2009 ◽  
pp. 1644 ◽  
Author(s):  
Madhab C. Das ◽  
Sujit K. Ghosh ◽  
E. Carolina Sañudo ◽  
Parimal K. Bharadwaj
Keyword(s):  
Transition Metals ◽  
Coordination Polymers ◽  
Alkaline Earth ◽  
Tricarboxylic Acid ◽  
X Ray

Two novel alkaline earth coordination polymers constructed from cinnamic acid and 1,10-phenanthroline: synthesis and structural and thermal properties

2018 ◽  
Vol 74 (2) ◽  
pp. 240-247 ◽  
Author(s):  
Nassima Bendjellal ◽  
Chahrazed Trifa ◽  
Sofiane Bouacida ◽  
Chaouki Boudaren ◽  
Mhamed Boudraa ◽  
...  
Keyword(s):  
Hydrogen Bonds ◽  
Coordination Polymers ◽  
Crystal Engineering ◽  
Alkaline Earth ◽  
Three Dimensional ◽  
X Ray Diffraction ◽  
Hydrothermal Conditions ◽  
X Ray ◽  
Carboxylate Groups ◽  
A Chain

In coordination chemistry and crystal engineering, many factors influence the construction of coordination polymers and the final frameworks depend greatly on the organic ligands used. The diverse coordination modes of N-donor ligands have been employed to assemble metal–organic frameworks. Carboxylic acid ligands can deprotonate completely or partially when bonding to metal ions and can also act as donors or acceptors of hydrogen bonds; they are thus good candidates for the construction of supramolecular architectures. We synthesized under reflux or hydrothermal conditions two new alkaline earth(II) complexes, namely poly[(1,10-phenanthroline-κ2N,N′)bis(μ-3-phenylprop-2-enoato-κ3O,O′:O)calcium(II)], [Ca(C10H7O2)2(C10H8N2)]n, (1), and poly[(1,10-phenanthroline-κ2N,N′)(μ3-3-phenylprop-2-enoato-κ4O:O,O′:O′)(μ-3-phenylprop-2-enoato-κ3O,O′:O)barium(II)], [Ba(C10H7O2)2(C10H8N2)]n, (2), and characterized them by FT–IR and UV–Vis spectroscopies, thermogravimetric analysis (TGA) and single-crystal X-ray diffraction analysis, as well as by powder X-ray diffraction (PXRD) analysis. Complex (1) features a chain topology of type 2,4 C4, where the Ca atoms are connected by O and N atoms, forming a distorted bicapped trigonal prismatic geometry. Complex (2) displays chains of topology type 2,3,5 C4, where the Ba atom is nine-coordinated by seven O atoms of bridging/chelating carboxylate groups from two cinnamate ligands and by two N atoms from one phenanthroline ligand, forming a distorted tricapped prismatic arrangement. Weak C—H...O hydrogen bonds and π–π stacking interactions between phenanthroline ligands are responsible to the formation of a supramolecular three-dimensional network. The thermal decompositions of (1) and (2) in the temperature range 297–1173 K revealed that they both decompose in three steps and transform to the corresponding metal oxide.

Two new CdII and ZnII coordination polymers incorporating 1-aminobenzene-3,4,5-tricarboxylic acid: synthesis, crystal structure and characterization

2019 ◽  
Vol 75 (8) ◽  
pp. 1065-1072 ◽  
Author(s):  
Zhi-Chao Shao ◽  
Xiang-Ru Meng ◽  
Hong-Wei Hou
Keyword(s):  
Coordination Polymers ◽  
Network Structure ◽  
Metal Ion ◽  
Acid Synthesis ◽  
Tricarboxylic Acid ◽  
Two Dimensional ◽  
X Ray Diffraction ◽  
X Ray ◽  
Rich Variety ◽  
Dimensional Network

Aminobenzoic acid derivatives are widely used in the preparation of new coordination polymers since they contain O-atom donors, as well as N-atom donors, and have a rich variety of coordination modes which can lead to polymers with intriguing structures and interesting properties. Two new coordination polymers incorporating 1-aminobenzene-3,4,5-tricarboxylic acid (H3abtc), namely, poly[(μ3-1-amino-5-carboxybenzene-3,4-dicarboxylato)diaquacadmium(II)], [Cd(C9H5NO6)(H2O)2] n , (I), and poly[[bis(μ5-1-aminobenzene-3,4,5-tricarboxylato)triaquatrizinc(II)] dihydrate], {[Zn3(C9H4NO6)2(H2O)3]·2H2O} n , (II), have been prepared and structurally characterized by single-crystal X-ray diffraction. In polymer (I), each tridentate 1-amino-5-carboxybenzene-3,4-dicarboxylate (Habtc2−) ligand coordinates to three CdII ions to form a two-dimensional network structure, in which all of the CdII ions and Habtc2− ligands are equivalent, respectively. Polymer (II) also exhibits a two-dimensional network structure, in which three crystallographically independent ZnII ions are bridged by two crystallographically independent pentadentate 1-aminobenzene-3,4,5-tricarboxylate (abtc3−) ligands. This indicates that changing the metal ion can influence the coordination mode of the H3abtc-derived ligand and further influence the detailed architecture of the polymer. Moreover, the IR spectra, thermogravimetric analyses and fluorescence properties were investigated.

Linear alkaline earth metal phosphinate coordination polymers: synthesis and structural characterization

2014 ◽  
Vol 70 (3) ◽  
pp. 602-607 ◽  
Author(s):  
Jeffrey A. Rood ◽  
Ashley L. Huttenstine ◽  
Zachery A. Schmidt ◽  
Michael R. White ◽  
Allen G. Oliver
Keyword(s):  
Coordination Polymers ◽  
Alkaline Earth ◽  
Linear Chain ◽  
Earth Metal ◽  
Alkaline Earth Metal ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Elemental Analyses ◽  
Ft Ir

Reaction of alkaline earth metal salts with diphenylphosphinic acid in dimethylformamide solvent afforded four coordination polymers: [Mg3(O2PPh2)6(DMF)2]·2DMF (I), [Ca(O2PPh2)2(DMF)2] (II), [Sr(O2PPh2)2(DMF)2] (III) and [Ba(O2PPh2)2(DMF)2] (IV) (where DMF isN,N-dimethylformamide). Single-crystal X-ray diffraction revealed that all four compounds produce linear chain structures in the solid state, with the Ca, Sr and Ba forming isostructural crystals. The bulk materials were characterized by FT–IR and1H NMR spectroscopy and elemental analyses.

Construction and photocatalytic properties of two metal-mediated coordination polymers based on benzene-1,3,5-tricarboxylic acid and trans-1-(pyridin-3-yl)-2-(pyridin-4-yl)ethene

2017 ◽  
Vol 73 (11) ◽  
pp. 1017-1023 ◽  
Author(s):  
Jing-Min Chen ◽  
Qian-Kun Zhou ◽  
Yi-Xuan Hou ◽  
Dong Liu
Keyword(s):  
Coordination Polymers ◽  
Organic Dyes ◽  
Rapid Development ◽  
Tricarboxylic Acid ◽  
Photocatalytic Properties ◽  
Supramolecular Network ◽  
Two Dimensional ◽  
X Ray Diffraction ◽  
Thermal Stabilities ◽  
X Ray

With the rapid development of modern industry, water pollution has become an intractable environmental issue facing humans worldwide. In particular, the organic dyes discharged into natural water from dyestuffs, dyeing and the textile industry are the main sources of pollution in wastewater. To eliminate these types of pollutants, degradation of organic contaminants through a photocatalytic technique is an effective methodology. To exploit more crystalline photocatalysts for the degradation of organic dyes, two coordination polymers, namely catena-poly[[(3,5-dicarboxybenzene-1-carboxylato-κO 1)silver(I)]-μ-trans-1-(pyridin-3-yl)-2-(pyridin-4-yl)ethene-κ2 N:N′], [Ag(C9H5O6)(C12H10N2)] n or [Ag(H2BTC)(3,4′-bpe)] n , (I), and poly[[(μ3-5-carboxybenzene-1,3-dicarboxylato-κ4 O 1,O 1′:O 3:O 3)[μ-trans-1-(pyridin-3-yl)-2-(pyridin-4-yl)ethene-κ2 N:N′]cadmium(II)] monohydrate], {[Cd(C9H4O6)(C12H10N2)]·H2O} n or {[Cd(HBTC)(3,4′-bpe)]·H2O} n , (II), have been prepared by the hydrothermal reactions of benzene-1,3,5-tricarboxylic acid (H3BTC) and trans-1-(pyridin-3-yl)-2-(pyridin-4-yl)ethene (3,4′-bpe) in the presence of AgNO3 or Cd(NO3)2·4H2O, respectively. These two title compounds have been structurally characterized by IR spectroscopy, elemental analysis, single-crystal X-ray diffraction and powder X-ray diffraction. In (I), the AgI ions and organic ligands form a one-dimensional coordination chain, and adjacent coordination chains are connected by Ag...O interactions to give rise to a two-dimensional supramolecular network. Each two-dimensional network is entangled with other equivalent networks to generate an infrequent interlocked 2D→3D (2D and 3D are two- and three-dimensional, respectively) supramolecular framework. In (II), the CdII ions are bridged by the HBTC2− and 3,4′-bpe ligands, which lie across centres of inversion, to give a two-dimensional coordination network. The thermal stabilities and photocatalytic properties of the title compounds have also been studied.

scholarly journals Pyrene Carboxylate Ligand Based Coordination Polymers for Microwave-Assisted Solvent-Free Cyanosilylation of Aldehydes

Molecules ◽  
2021 ◽  
Vol 26 (4) ◽  
pp. 1101
Author(s):  
Anirban Karmakar ◽  
Anup Paul ◽  
Elia Pantanetti Sabatini ◽  
M. Fátima C. Guedes da Silva ◽  
Armando J. L. Pombeiro
Keyword(s):  
Coordination Polymer ◽  
Single Crystal ◽  
Coordination Polymers ◽  
Metal Ion ◽  
Solvent Free ◽  
Lewis Acidity ◽  
Carboxylate Ligand ◽  
X Ray Diffraction ◽  
X Ray ◽  
Microwave Assisted

The new coordination polymers (CPs) [Zn(μ-1κO1:1κO2-L)(H2O)2]n·n(H2O) (1) and [Cd(μ4-1κO1O2:2κN:3,4κO3-L)(H2O)]n·n(H2O) (2) are reported, being prepared by the solvothermal reactions of 5-{(pyren-4-ylmethyl)amino}isophthalic acid (H2L) with Zn(NO3)2.6H2O or Cd(NO3)2.4H2O, respectively. They were synthesized in a basic ethanolic medium or a DMF:H2O mixture, respectively. These compounds were characterized by single-crystal X-ray diffraction, FTIR spectroscopy, thermogravimetric and elemental analysis. The single-crystal X-ray diffraction analysis revealed that compound 1 is a one dimensional linear coordination polymer, whereas 2 presents a two dimensional network. In both compounds, the coordinating ligand (L2−) is twisted due to the rotation of the pyrene ring around the CH2-NH bond. In compound 1, the Zn(II) metal ion has a tetrahedral geometry, whereas, in 2, the dinuclear [Cd2(COO)2] moiety acts as a secondary building unit and the Cd(II) ion possesses a distorted octahedral geometry. Recently, several CPs have been explored for the cyanosilylation reaction under conventional conditions, but microwave-assisted cyanosilylation of aldehydes catalyzed by CPs has not yet been well studied. Thus, we have tested the solvent-free microwave-assisted cyanosilylation reactions of different aldehydes, with trimethylsilyl cyanide, using our synthesized compounds, which behave as highly active heterogeneous catalysts. The coordination polymer 1 is more effective than 2, conceivably due to the higher Lewis acidity of the Zn(II) than the Cd(II) center and to a higher accessibility of the metal centers in the former framework. We have also checked the heterogeneity and recyclability of these coordination polymers, showing that they remain active at least after four recyclings.

scholarly journals Synthesis of New Derivatives of BEDT-TTF: Installation of Alkyl, Ethynyl, and Metal-Binding Side Chains and Formation of Tris(BEDT-TTF) Systems

2021 ◽  
Vol 7 (8) ◽  
pp. 110
Author(s):  
Songjie Yang ◽  
Matteo Zecchini ◽  
Andrew Brooks ◽  
Sara Krivickas ◽  
Desiree Dalligos ◽  
...  
Keyword(s):  
Metal Binding ◽  
Tricarboxylic Acid ◽  
Metal Salts ◽  
Side Chain ◽  
Side Chains ◽  
Ethynyl Group ◽  
X Ray ◽  
Transition Metal Salts ◽  
Alkyl Side Chains ◽  
Derivatives Of

The syntheses of new BEDT-TTF derivatives are described. These comprise BEDT-TTF with one ethynyl group (HC≡C-), with two (n-heptyl) or four (n-butyl) alkyl side chains, with two trans acetal (-CH(OMe)2) groups, with two trans aminomethyl (-CH2NH2) groups, and with an iminodiacetate (-CH2N(CH2CO2−)2 side chain. Three transition metal salts have been prepared from the latter donor, and their magnetic properties are reported. Three tris-donor systems are reported bearing three BEDT-TTF derivatives with ester links to a core derived from benzene-1,3,5-tricarboxylic acid. The stereochemistry and molecular structure of the donors are discussed. X-ray crystal structures of two BEDT-TTF donors are reported: one with two CH(OMe)2 groups and with one a -CH2N(CH2CO2Me)2 side chain.

scholarly journals Metal(II) Coordination Polymers from Tetracarboxylate Linkers: Synthesis, Structures, and Catalytic Cyanosilylation of Benzaldehydes

Catalysts ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 204
Author(s):  
Yu Li ◽  
Chumin Liang ◽  
Xunzhong Zou ◽  
Jinzhong Gu ◽  
Marina V. Kirillova ◽  
...  
Keyword(s):  
Coordination Polymers ◽  
Polycarboxylic Acid ◽  
X Ray Diffraction ◽  
X Ray ◽  
Trimethylsilyl Cyanide ◽  
Effect Of Solvent ◽  
Highly Active ◽  
Solvent Type ◽  
Metal Organic ◽  
Chloride Salts

Three 2D coordination polymers, [Cu2(µ4-dpa)(bipy)2(H2O)]n∙6nH2O (1), [Mn2(µ6-dpa)(bipy)2]n (2), and [Zn2(µ4-dpa)(bipy)2(H2O)2]n·2nH2O (3), were prepared by a hydrothermal method using metal(II) chloride salts, 3-(2′,4′-dicarboxylphenoxy)phthalic acid (H4dpa) as a linker, as well as 2,2′-bipyridine (bipy) as a crystallization mediator. Compounds 1–3 were obtained as crystalline solids and fully characterized. The structures of 1–3 were established by single-crystal X-ray diffraction, revealing 2D metal-organic networks of sql, 3,6L66, and hcb topological types. Thermal stability and catalytic behavior of 1–3 were also studied. In particular, zinc(II) coordination polymer 3 functions as a highly active and recoverable heterogeneous catalyst in the mild cyanosilylation of benzaldehydes with trimethylsilyl cyanide to give cyanohydrin derivatives. The influence of various parameters was investigated, including a time of reaction, a loading of catalyst and its recycling, an effect of solvent type, and a substrate scope. As a result, up to 93% product yields were attained in a catalyst recoverable and reusable system when exploring 4-nitrobenzaldehyde as a model substrate. This study contributes to widening the types of multifunctional polycarboxylic acid linkers for the design of novel coordination polymers with notable applications in heterogeneous catalysis.

scholarly journals Multidimensional Ln-Aminophthalate Photoluminescent Coordination Polymers

Materials ◽  
2021 ◽  
Vol 14 (7) ◽  
pp. 1786
Author(s):  
Carla Queirós ◽  
Chen Sun ◽  
Ana M. G. Silva ◽  
Baltazar de Castro ◽  
Juan Cabanillas-Gonzalez ◽  
...  
Keyword(s):  
Water Content ◽  
Coordination Polymers ◽  
Metal Ion ◽  
Low Cost ◽  
Microwave Assisted Synthesis ◽  
X Ray Diffraction ◽  
X Ray ◽  
Wide Range ◽  
Ft Ir ◽  
Ft Ir Spectroscopy

The development of straightforward reproducible methods for the preparation of new photoluminescent coordination polymers (CPs) is an important goal in luminescence and chemical sensing fields. Isophthalic acid derivatives have been reported for a wide range of applications, and in addition to their relatively low cost, have encouraged its use in the preparation of novel lanthanide-based coordination polymers (LnCPs). Considering that the photoluminescent properties of these CPs are highly dependent on the existence of water molecules in the crystal structure, our research efforts are now focused on the preparation of CP with the lowest water content possible, while considering a green chemistry approach. One- and two-dimensional (1D and 2D) LnCPs were prepared from 5-aminoisophthalic acid and Sm3+/Tb3+ using hydrothermal and/or microwave-assisted synthesis. The unprecedented LnCPs were characterized by single-crystal X-ray diffraction (SCRXD), powder X-ray diffraction (PXRD), Fourier transform infrared (FT-IR) spectroscopy and scanning electron microscopy (SEM), and their photoluminescence (PL) properties were studied in the solid state, at room temperature, using the CPs as powders and encapsulated in poly(methyl methacrylate (PMMA) films, envisaging the potential preparation of devices for sensing. The materials revealed interesting PL properties that depend on the dimensionality, metal ion, co-ligand used and water content.

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