scholarly journals New Copper(II) Coordination Compounds Assembled from Multifunctional Pyridine-Carboxylate Blocks: Synthesis, Structures, and Catalytic Activity in Cycloalkane Oxidation

Molecules ◽  
2018 ◽  
Vol 24 (1) ◽  
pp. 6 ◽  
Author(s):  
Na Zhao ◽  
Yu Li ◽  
Jinzhong Gu ◽  
Tiago Fernandes ◽  
Marina Kirillova ◽  
...  

Two new copper(II) coordination compounds, namely a 1D coordination polymer [Cu(µ-cpna)(phen)(H2O)]n (1) and a discrete tetracopper(II) derivative [Cu(phen)2(H2O)]2[Cu2(µ-Hdppa)2(Hdppa)2] (2), were hydrothermally synthesized from copper(II) chloride as a metal source, 5-(4-carboxyphenoxy)nicotinic acid (H2cpna) or 5-(3,4-dicarboxylphenyl)picolinic acid (H3dppa) as a principal building block, and 1,10-phenanthroline (phen) as a crystallization mediator. Compounds 1 and 2 were isolated as air-stable microcrystalline solids and fully characterized by elemental and thermogravimetric analyses, IR spectroscopy, powder and single-crystal X-ray diffraction. In the solid state, the structure of 1 discloses the linear interdigitated 1D coordination polymer chains with the 2C1 topology. The crystal structure of an ionic derivative 2 shows that the mono- and dicopper(II) units are extended into the intricate 1D hydrogen-bonded chains with the SP 1-periodic net (4,4)(0,2) topology. Thermal stability and catalytic properties of 1 and 2 were also investigated. In fact, both Cu derivatives act as efficient homogeneous catalysts (catalyst precursors) for the mild oxidation of cycloalkanes by hydrogen peroxide to give the corresponding alcohols and ketones; the substrate scope and the effects of type and amount of acid promoter as well as bond-, regio-, and stereo-selectivity features were investigated.

1997 ◽  
Vol 52 (1) ◽  
pp. 125-134 ◽  
Author(s):  
Rolf W. Saalfrank ◽  
Roland Harbig ◽  
Oliver Struck ◽  
Frank Hampel ◽  
Eva Maria Peters ◽  
...  

Reaction of a methanolic copper(II) acetate solution with tetrazolyl enol derivatives 2a or 2b leads to the formation of the corresponding lD-coordination polymer 1∞[CuL2] 3a and pseudo 1D-coordination polymer [CuL2]2 3b, respectively. On the contrary, reaction of 2c with methanolic copper(II) acetate solution yields OH-bridged 1D-coordination polymer 1∞[CuL2(MeOH)2 3c. Single-crystal X-ray diffraction of the supramolecular species 3 established unequivocally the structures of the stairlike coordination compounds. Reaction of a methanolic copper(II) acetate solution with amidotetrazole derivative 6 leads to the formation of the lD-coordination polymer 1∞ [CuL2] 7. The structure of 7 has been established by X-ray structure analysis


2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Xin-Yue Zhang ◽  
Chen Zhang ◽  
Jun Wang ◽  
Xiao-Juan Xu

Abstract A new 2-dimensional (2D) zinc(II) coordination polymer based on a flexible bis(imidazole) ligand, namely, [Zn2(BIBP)(BPDC)2·DMF] n (1) BIBP is 1,4-bis(4-(imidazole-1-yl)benzyl)piperazine and H2BPDC is benzophenone-2,4′-dicarboxylic acid), has been synthesized and characterized through single-crystal X-ray diffraction, infrared (IR) spectroscopy, and elemental and thermal gravimetric analysis. Complex 1 exhibits a 2D framework oriented parallel to [0 2 1] based on [Zn(BPDC)] n chains. The fluorescence and catalytic properties of complex 1 for the photodegradation of methylene blue were investigated.


2006 ◽  
Vol 59 (1) ◽  
pp. 40 ◽  
Author(s):  
Luís Cunha-Silva ◽  
Ruksanna Ahmad ◽  
Michaele J. Hardie

New crystalline coordination networks based on Ag(i) and N-bridging ligands — pyrazine (pyz), 4,4′-bipyridine (bpy), and 2,3-bis-(2-pyridyl)pyrazine (bppz) — incorporating carborane monoanions (CB11H12)− or [Co(C2B9H11)2]− were isolated and characterized using single crystal X-ray diffraction, microanalysis, and infrared spectroscopy. All the complexes with the bpy and bppz ligands reveal 1D coordination infinite chains involving the Ag(i) and the ligands, and layered extended structures with rows of carborane anions between the layers of chains. Interestingly, two polymorphs of the complex [Ag(bpy)(CH3CN)][Co(C2B9H11)2] were observed. The complex [Ag(pyz)(CH3CN)2][Co(C2B9H11)2] shows a 1D coordination polymer, while the pyz complex with the smaller carborane anion {[Ag(pyz)](CB11H12)} exhibits a 3D coordination network structure with four Ag···H−B interactions between the silver centre and carborane anions.


2012 ◽  
Vol 77 (1) ◽  
pp. 67-73 ◽  
Author(s):  
Masoud Mirzaei ◽  
Hossein Eshtiagh-Hosseini ◽  
Azam Hassanpoor ◽  
Victor Barba

The new 1D-coordination polymer of CuII ion, {(2- apymH)2[Cu(pyzdc)2] .6H2O}n, (2-apym = 2-aminopyrimidine, pyzdcH2 = 1,4- pyrazine-2,3-dicarboxylic acid), was synthesized based on proton transfer mechanism and characterized by elemental analysis, infrared spectroscopy, and single crystal X-ray diffraction. The coordination polymer consists of infinite anionic chains of [Cu(pyzdc)2]2- anion bridged crossing double chain running along a-axis and discrete (2-apymH)+ fragment. The CuII ion is located on inversion centre in the basal plane of an elongated octahedron and two oxygen atoms from adjacent (pyzdc)2-ligands occupy axial position. The interaction between oxygen atoms of water molecules along with the dicarboxylic acid play an important role in the overall supramolecular assembly.


Polymers ◽  
2019 ◽  
Vol 11 (7) ◽  
pp. 1224 ◽  
Author(s):  
Dalila Rocco ◽  
Alessandro Prescimone ◽  
Y. Klein ◽  
Dariusz Gawryluk ◽  
Edwin Constable ◽  
...  

The synthesis and characterization of 4′-(4-methoxyphenyl)-3,2′:6′,3″-terpyridine (2) (IUPAC PIN 24-(4-methoxyphenyl)-12,22:26,32-terpyridine) are described, and its coordination behaviour with cobalt(II) thiocyanate has been investigated. In a series of experiments, crystals were grown at room temperature by layering a MeOH solution of Co(NCS)2 over a CHCl3 solution of 2 using 1:1, 1:2 or 2:1 molar ratios of metal salt-to-ligand. Crystals harvested within 2–3 weeks proved to be the 1D-coordination polymer [Co(2)(NCS)2(MeOH)2]n and powder X-ray diffraction (PXRD) confirmed that the crystals selected for single-crystal X-ray diffraction were representative of the bulk samples. Longer crystallization times with a Co(NCS)2 to 2 molar ratio of 1:1 yielded crystals of [Co(2)(NCS)2(MeOH)2]n (1D-chain) and the pseudopolymorphs [{Co(2)2(NCS)2}·3MeOH]n and [{Co(2)2(NCS)2}·2.2CHCl3]n ((4,4)-nets), each type of crystal originating from a different zone in the crystallization tube. PXRD for this last experiment confirmed that the dominant product in the bulk sample was the 1D-coordination polymer.


2021 ◽  
Vol 9 ◽  
Author(s):  
Campbell F. R. Mackenzie ◽  
Lucie Delforce ◽  
D. Rota Martir ◽  
David B. Cordes ◽  
Alexandra M. Z. Slawin ◽  
...  

[2.2]Paracyclophane scaffolds have seen limited use as building blocks in supramolecular chemistry. Here, we report the synthesis and characterization of a 1D coordination polymer consisting of silver(I) ions bound to a [2.2]paracyclophane scaffold functionalized with two 4-pyridyl units. The structure of the polymer has been determined from single crystal X-ray diffraction analysis and reveals two different silver coordination motifs that alternate along the 1D coordination polymer. The coordination polymer exhibits strong blue and sky-blue fluorescence in solution and in the crystalline solid state, respectively.


1996 ◽  
Vol 61 (8) ◽  
pp. 1131-1140 ◽  
Author(s):  
Abd El-Aziz Ahmed Said

Vanadium oxide catalysts doped or mixed with 1-50 mole % Fe3+ ions were prepared. The structure of the original samples and those calcined from 200 up to 500 °C were characterized by TG, DTA, IR and X-ray diffraction. The SBET values and texture of the solid catalysts were investigated. The catalytic dehydration-dehydrogenation of isopropanol was carried out at 200 °C using a flow system. The results obtained showed an observable decrease in the activity of V2O5 on the addition of Fe3+ ions. Moreover, Fe2V4O13 is the more active and selective catalyst than FeVO4 spinels. The results were correlated with the active sites created on the catalyst surface.


2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Xinzhao Xia ◽  
Lixian Xia ◽  
Geng Zhang ◽  
Yuxuan Jiang ◽  
Fugang Sun ◽  
...  

Abstract In this work, a new type of zinc(II) coordination polymer {[Zn(HIDC)(BBM)0.5]·H2O} n (Zn-CP) was synthesized using 4,5-imidazoledicarboxylic acid (H3IDC) and 2,2-(1,4-butanediyl)bis-1,3-benzimidazole (BBM) under hydrothermal conditions. Its structure has been characterized by infrared spectroscopy, elemental analysis and single crystal X-ray diffraction analysis. The Zn(II) ion is linked by the HIDC2− ligand to form a zigzag chain by chelating and bridging, and then linked by BBM to form a layered network structure. Adjacent layers are further connected by hydrogen bond interaction to form a 3-D supramolecular framework. The solid-state fluorescence performance of Zn-CP shows that compared with free H3IDC ligand, its fluorescence intensity is significantly enhanced.


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

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.


Molecules ◽  
2021 ◽  
Vol 26 (11) ◽  
pp. 3358
Author(s):  
Sadaf Rauf ◽  
Agata Trzesowska-Kruszynska ◽  
Tomasz Sierański ◽  
Marcin Świątkowski

Three new copper coordination compounds derived from 2,2-bis(hydroxymethyl)propionic acid (dmpa) and hexamethylenetetramine (hmta) were obtained and their crystal structures were determined. The stoichiometry of the reagents applied in the syntheses reflects the metal to ligand molar ratio in the formed solid products. Due to the multiple coordination modes of the used ligands, wide structural diversity was achieved among synthesized compounds, i.e., mononuclear [Cu(dmp)2(hmta)2(H2O)] (1), dinuclear [Cu2(dmp)4(hmta)2] (2), and 1D coordination polymer [Cu2(dmp)4(hmta)]n (3). Their supramolecular structures are governed by O—H•••O and O—H•••N hydrogen bonds. The compounds were characterized in terms of absorption (UV-Vis and IR) and thermal properties. The relationships between structural features and properties were discussed in detail. Owing to discrepancies in the coordination mode of a dmp ligand, bidentate chelating in 1, and bidentate bridging in 2 and 3, there is a noticeable change in the position of the bands corresponding to the stretching vibrations of the carboxylate group in the IR spectra. The differences in the structures of the compounds are also reflected in the nature and position of the UV-Vis absorption maxima, which are located at lower wavelengths for 1.


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