Structural Diversity and Properties of Six ZnII/CdII Coordination Polymers Based on an O-Bridged Semi-Rigid Bis-pyridyl-bis-amide and Different Dicarboxylates

2016 ◽  
Vol 69 (8) ◽  
pp. 846 ◽  
Author(s):  
Xiu-Li Wang ◽  
Xiao-Mei Wu ◽  
Guo-Cheng Liu ◽  
Nai-Li Chen ◽  
Hong-Yan Lin ◽  
...  
Keyword(s):  
Coordination Polymers ◽  
Structural Diversity ◽  
Solvothermal Reaction ◽  
Central Metal ◽  
X Ray Diffraction ◽  
X Ray ◽  
Left Handed ◽  
Linear Chains ◽  
Benzenedicarboxylic Acid ◽  
N Wave

Six new coordination polymers [Zn2(L)(chdc)2]·2H2O (1), [Zn(L)(mip)]·3H2O (2), [Zn(L)(bdc)]·H2O (3), [Cd2(L)(chdc)2]·2H2O (4), [Cd(L)(mip)]·2H2O (5), and [Cd(L)(bdc)]·2H2O (6) (L = N,N′-bis(pyridine-3-yl)-4,4′-oxybis(benzoic) dicarboxamide, 1,4-H2chdc = trans-1,4-cyclohexanedicarboxylic acid, H2mip = 5-methylisophthalic acid, 1,3-H2bdc = 1,3-benzenedicarboxylic acid) have been synthesized from ZnII/CdII ions and L ligands in the presence of auxiliary dicarboxylates via hydrothermal or solvothermal reaction. The coordination polymers have been fully characterized by infrared spectroscopy, powder X-ray diffraction, thermogravimetric analyses, and single-crystal X-ray diffraction analysis. Complex 1 contains a 1D [Zn4(chdc)4]n wave-like chain, which is connected by the μ2-bridging ligand L, affording a 3,4-connected 2D polymeric network. Complexes 2 and 3 both possess similar 2D 4-connected square grid-like layers, which are based on Zn-carboxylates linear chains and left-handed [Zn(L)]n helix chains. The structure of complex 4 is very similar to that of 1. Complexes 5 and 6 demonstrate a similar 2D 3,5-connected channel-level network, which is constructed from a pair of Cd-carboxylates linear chains and 1D [Cd2(L)2]n cyclic chains. The effects of the central metal ions and different dicarboxylates on the formation and structures of the title coordination polymers have been discussed. In addition, the fluorescence and photocatalytic properties of the title complexes have been investigated.

Assembly of Three Lanthanide Coordination Polymers from 2-(4-Carboxybenzyloxy) Benzoic Acid Ligand: Synthesis, Structure, and Fluorescent Properties

2020 ◽  
Vol 73 (1) ◽  
pp. 16
Author(s):  
Shu-Ju Wang ◽  
Yi-Hui Jiang ◽  
Han-Lin Wu ◽  
Li-Xin You ◽  
Gang Xiong ◽  
...  
Keyword(s):  
Benzoic Acid ◽  
Single Crystal ◽  
Coordination Polymers ◽  
Lanthanide Ions ◽  
Solvothermal Reaction ◽  
X Ray Diffraction ◽  
Fluorescent Properties ◽  
Single Crystal Diffraction ◽  
X Ray ◽  
1D Chain

Three new coordination polymers, {[Ln(cbb)(Hcbb)(DMF)·H2O]n, Ln=Sm (1), Eu (2), Tb(3), H2cbb=2-(4-carboxybenzyloxy) benzoic acid, DMF=N,N-dimethylformamide}, have been synthesised by a solvothermal reaction and structurally characterised by infrared spectroscopy, elemental analysis, thermogravimetry analysis, and X-ray single-crystal diffraction. The results of single-crystal X-ray diffraction indicate that the coordination polymers 1–3 are isostructural, belong to a triclinic system, space group P-1, and show 1D chain structures through the H2cbb ligands connecting adjacent lanthanide ions. In addition, the fluorescence properties of polymers 1–3 were also investigated.

scholarly journals Structural diversity induced by ligand geometry: From two-dimensional to three-dimensional coordination polymers with pyridine

2020 ◽  
pp. 174751982096816
Author(s):  
Fang-Kuo Wang ◽  
Shi-Yao Yang ◽  
Hua-Ze Dong
Keyword(s):  
Coordination Polymers ◽  
Three Dimensional ◽  
Structural Diversity ◽  
Dimensional Structure ◽  
Layer By Layer ◽  
Two Dimensional ◽  
Guest Molecules ◽  
X Ray ◽  
Benzenedicarboxylic Acid ◽  
Benzenetricarboxylic Acid

Two coordination polymers with two-dimensional and three-dimensional structures are, {[Zn3(bdc)3(py)2]·2NMP}n (1) (H2bdc = 1,4-benzenedicarboxylic acid) and [Zn2(NO3−)(btc)(nmp)2(py)]n (2) (H3btc = 1,3,5-benzenetricarboxylic acid), synthesized by hot-solution reactions of Zn(NO3)2·6H2O, pyridine (py) and two different ligands in N-methylpyrrolidone (NMP). {[Zn3(bdc)3(py)2]·2NMP}n exhibits two-dimensional networks with trizinc subunits [Zn3(COO)6py2] stacking with a layer-by-layer alignment, and there are strong π–π interactions involving py from adjacent layers. [Zn2(NO3−)(btc)(nmp)2(py)]n has a three-dimensional structure containing two independent zinc ions, tetrahedral ZnO4 and octahedral ZnNO5. Based on X-ray studies, the coordination polymers {[Zn3(bdc)3(py)2]·2NMP}n (1) have a porous structure with NMP guest molecules. In contrast, X-ray studies revealed that coordination polymer [Zn2(NO3−)(btc)(nmp)2(py)]n (2) had a larger void that was inhabited by coordinated py and NMP. In addition, the form of the two coordination polymers changed from two-dimensional to three-dimensional with transformation of the ligand geometry.

Five bis(imidazole)-based Coordination Polymers Tuned by Central Metal Ions and S-containing Dicarboxylates: Syntheses, Structures, and Properties

2013 ◽  
Vol 66 (11) ◽  
pp. 1370 ◽  
Author(s):  
Xiu-Li Wang ◽  
Yun Qu ◽  
Guo-Cheng Liu ◽  
Jing-Jing Huang ◽  
Nai-Li Chen ◽  
...  
Keyword(s):  
Coordination Polymers ◽  
Dye Degradation ◽  
Luminescent Properties ◽  
Central Metal ◽  
X Ray Diffraction ◽  
Hydrothermal Conditions ◽  
X Ray ◽  
Structures And Properties ◽  
Ring Complex ◽  
3D Architecture

Five new coordination polymers, namely [Zn(2-CMSN)(biim-4)] (1), [Co2(2-CMSN)2(biim-4)(H2O)4] (2), [Ni(2-CMSN)(biim-4)0.5(H2O)2] (3), [Cd(2-CMSN)(biim-4)0.5(H2O)2] (4), and [Cd(ADTZ)(biim-4)1.5]·5H2O (5), (2-H2CMSN = 2-carboxymethylsulfanyl nicotinic acid, H2ADTZ = 2,5-(S-acetic acid) dimercapto-1,3,4-thiadiazole, biim-4 = 1,1′-(1,4-butanediyl)bis(imidazole)) have been synthesised under hydrothermal conditions and structurally characterised by single-crystal X-ray diffraction analysis, infrared spectroscopy, elemental analysis, thermogravimetric analysis, and powder X-ray diffraction. Complex 1 shows a 2D undulated sheet, which is constructed from 1D meso-helical [Zn-(biim-4)]n chains and linear [Zn-(2-CMSN)]n chains. Complexes 2–4 exhibit a similar 2D (4,4) grid network constructed from zigzag [M-(2-CMSN)]n chains and linear [M-(biim-4)]n chains (M = CoII, NiII and CdII), which possesses a ‘4+2’ type six-membered ring. Complex 5 displays a 3D architecture derived from 2D Cd-(biim-4) layers and double ADTZ linkers with diamond-type 66 topology. The effects of the central metals and S-containing dicarboxylates on the structures of the title coordination polymers have been discussed. The luminescent properties of complexes 1, 4, and 5 have been studied. Complex 5 exhibits photocatalytic activity for dye degradation under ultraviolet light and good stability towards photocatalysis.

Three Mn(II) metal organic frameworks with the same chemical compositions, but different topological structures and properties

CrystEngComm ◽  
2021 ◽  
Author(s):  
Li Tian ◽  
Zhi Long Ma ◽  
Mengchen Wang ◽  
Jian Yun Shi
Keyword(s):  
Coordination Polymers ◽  
Terephthalic Acid ◽  
Metal Organic Frameworks ◽  
Solvothermal Reaction ◽  
Chemical Compositions ◽  
X Ray Diffraction ◽  
X Ray ◽  
Multidentate Ligand ◽  
Structures And Properties ◽  
Metal Organic

Solvothermal reaction of a novel multidentate ligand 2,5-bis-(1,2,4-triazol-1-yl)-terephthalic acid (H2TTPA), with MnCl2 afforded three structurally different coordination polymers with the similar formula [Mn(TTPA)•H2O]n (Mn-(1-3)). Single-crystal X-ray diffraction analyses show that...

Anion Effect on the Structural Diversity of 1-D and 2-D Zinc(II) Coordination Polymers with a Flexible Fluorinated Bis(imidazole) Ligand

2014 ◽  
Vol 69 (8) ◽  
pp. 878-884 ◽  
Author(s):  
Feng Tian ◽  
Hong-Dan Wang ◽  
Ming-Yang He ◽  
Qun Chen ◽  
Sheng-Chun Chen
Keyword(s):  
Coordination Polymers ◽  
Structural Diversity ◽  
Coordination Geometry ◽  
Tetrahedral Coordination ◽  
X Ray Diffraction ◽  
X Ray ◽  
Anion Effect ◽  
Structural Differences ◽  
The Difference ◽  
Cationic Network

Reactions of a flexible fluorinated ligand, 2,3,5,6-tetrafluoro-1,4-bis(imidazol-1-ylmethyl) benzene (Fbix), with ZnX2 (X =OAc- or NO3-) lead to the formation of the two new ZnII coordination polymers [Zn(Fbix)(OAc)2]n (1) and {[Zn2(Fbix)3(NO3)2](NO3)2(H2O)3}n (2), which have been characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. Although the ZnII centers of both 1 and 2 are in a similar tetrahedral coordination geometry, each ZnII ion in 1 is surrounded by two Fbix spacers and two terminal OAc- anions to form a highly undulated chain, whereas each ZnII ion in 2 is embraced by three Fbix ligands and one NO3- anion to result in a two-dimensional cationic network. Since 1 and 2 are synthesized under the same conditions, the structural differences between them are attributable to the difference of the counterions. The solid-state properties such as thermal stability and luminescence of 1 and 2 have also been studied briefly.

A New 2D Zinc(II)-Organic Framework with Dinuclear Units Based on Iodinated Terephthalate: Synthesis, Crystal Structure and Luminescence Behavior

2014 ◽  
Vol 69 (8) ◽  
pp. 859-863 ◽  
Author(s):  
Kai Cui ◽  
Ji Ma ◽  
Xian-Kuan Huo ◽  
Jian-Xun Zhang
Keyword(s):  
Three Dimensional ◽  
Solvothermal Reaction ◽  
Two Dimensional ◽  
X Ray Diffraction ◽  
X Ray ◽  
Dimensional Network ◽  
Benzenedicarboxylic Acid ◽  
Secondary Building Units ◽  
Thermal Stability Of ◽  
Luminescence Behavior

A new coordination polymer [Zn(BDC-I2)(DMF)]n (1) has been prepared by solvothermal reaction of Zn(II) nitrate with 2,5-diiodo-1,4-benzenedicarboxylic acid (H2BDC-I2) in ethanol-DMF, and characterized by elemental analysis, IR spectroscopy and single-crystal and powder X-ray diffraction techniques. Complex 1 shows a two-dimensional network possessing dinuclear Zn2(CO2)4 secondary building units, which are further assembled into a three-dimensional supramolecular structure through intermolecular C-H···I interactions. Solid-state properties such as photoluminescence and thermal stability of 1 have also been investigated.

Synthesis, Crystal Structure, and Photoluminescent Properties of a Series of LnIII–CuI Heterometallic Coordination Polymers Based on Cu4I3 Clusters and Ln–ina Rod Units

2017 ◽  
Vol 70 (8) ◽  
pp. 943 ◽  
Author(s):  
Chengcai Xia ◽  
Gang Xiong ◽  
Lixin You ◽  
Baoyi Ren ◽  
Shuju Wang ◽  
...  
Keyword(s):  
Coordination Polymers ◽  
Light Emission ◽  
Isonicotinic Acid ◽  
Synergistic Effects ◽  
Green Light ◽  
Lanthanide Ions ◽  
Solvothermal Reaction ◽  
X Ray Diffraction ◽  
X Ray ◽  
Heterometallic Coordination Polymers

A novel series of LnIII–CuI heterometallic coordination polymers (HCPs) {[Ln2Cu4I3(ina)7(DMA)2]n·nDMA, Ln = La (1), Ce (2), Pr (3) Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9) Ho (10), Er (11), Yb (12), Hina = isonicotinic acid, DMA = N,N-dimethylacetamide} were synthesised by a solvothermal reaction. The structures of compounds 1–12 were characterised by elemental analysis, FT-IR spectroscopy, thermogravimetric analysis, and powder X-ray diffraction. Single crystal X-ray diffraction studies revealed that 1–12 are isomorphous and are 3D heterometallic coordination polymers based on inorganic Cu4I3 clusters and Ln2(ina)7(DMA) rod units. In addition, the luminescent properties of compounds 5–9 have been investigated in detail. All of them exhibited green light emission due to the synergistic effects of characteristic emissions of lanthanide ions and iodide-to-copper charge transfer.

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 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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