Cadmium Coordination Polymers Research Articles

2D coordination polymers of cadmium(II) and zinc(II) derived from N,N'-bis(glycinyl)pyromellitic diimide: microwave-assisted synthesis, structures, spectroscopic properties and influence of metal-ion size.

Two new two-dimensional (2D) coordination polymers (CPs), namely, poly[diaqua[μ4-2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetato-κ4O:O':O'':O''']cadmium(II)], [Cd(C14H6N2O8)(H2O)2]n (1), and poly[[tetraaqua[μ4-2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetato-κ4O:O':O'':O'''][μ2-2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetato-κ2O:O']dizinc(II)] dihydrate], {[Zn(C14H6N2O8(H2O)2]·H2O}n (2), have been synthesized by the microwave-irradiated reaction of Cd(CH3COO)2·2H2O and Zn(CH3COO)2·2H2O, respectively, with N,N'-bis(glycinyl)pyromellitic diimide {BGPD, namely, 2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetic acid, H2L}. In the crystal structure of 1, the CdII ion is six-coordinated by four carboxylate O atoms from four symmetry-related L2- dianions and two coordinated water molecules, furnishing an octahedral coordination geometry. The bridging L2- dianion links four symmetry-related CdII cations into a 2D layer-like structure with a 3,4-connected bex topology. In the crystal structure of 2, the ZnII ion is five-coordinated by three carboxylate O atoms from three different L2- dianions and two coordination water molecules, furnishing a trigonal bipyramidal coordination geometry. Two crystallographically independent ligands serve as μ4- and μ2-bridges, respectively, to connect the ZnII ions, thereby forming a 2D layer with a 3,3-connected hcb topology. Crystal structure analysis reveals the presence of n→π* interactions between two carbonyl groups of the pyromellitic diimide moieties in 1 and 2. CP 1 exhibits an enhanced fluorescence emission compared with free H2L. The framework of 2 decomposes from 720 K, indicating its high thermal stability. A comparative analysis of a series of structures based on the BGPD ligand indicates that the metal-ion size has a great influence on the connection modes of the metal ions due to different steric effects, which, in turn, affects the structures of the SBUs (secondary building units) and frameworks.

Practicality and Compatibility of Cd(II) Coordination Polymer as Luminescent Sensor in Selective and Sensitive Detection of 3‐Nitrotyrosine Biomarker

AbstractBased on the mixed ligands of 1,4‐bis(2,4,6‐tricarboxylpyrid‐5‐yl)benzene (H6BTPB) and 1,4‐bis(imidazol‐1‐yl)benzene (bib), a new cadmium(II) coordination polymer with the molecular formula of {[Cd(bib)(μ2‐H2O)(H2O)2](H4BTPB)0.5(bib)0.5}n (CdCP) was constructed under solvothermal condition, and displayed a 3D supramolecular structure expanded by the hydrogen bonds between the 1D [Cd(bib)(μ2‐H2O)(H2O)2]n ladder chain and the guests. Profiting from its superior stability and inherent luminescence, the prepared CdCP dispalyed great potential as a highly sensitive and selective luminescent sensor in trace detection of 3‐NT biomarker in both water and real bodily fluids through the luminescence quenching effects, with the Ksv and LODs being 2.408×105 M−1 and 30.3 nM in water, 2.230×105 M−1 and 44.7 nM in diluted urine, 2.249×105 M−1 and 43.9 nM in diluted serum, respectively. Subsequent mechanism studies indicated the synergistic effect of internal filtering effect, photo‐induced electron transfer, and fluorescence resonance energy transfer determining the luminescence quenching response of CdCP towards 3‐NT biomarker.

A comparative study of nickel and cadmium coordination polymers: Framework topology and proton conductivity

Two new coordination polymers (CPs), [Ni2(dip)2(obb)2]⋅2H2O, and [Cd2(dip)2(obb)2(H2O)]⋅5.5H2O, were successfully synthesized via hydrothermal processes utilizing the organic linkers 4,4′-oxybisbenzoate (obb) and 2,6-di(1H-imidazole-1-yl)pyridine (dip). The unique structures of both CPs were confirmed by single-crystal X-ray diffraction studies. Ni-CP presents an intricate three-fold interpenetrated 3D framework, featuring a rare cag topology centered around dinuclear nodes. In contrast, Cd-CP exhibits a distinctive non-interpenetrated 2D framework with an unusual kIa topology. Despite Cd-CP's water coordination and the inclusion of substantial guest water molecules, it unexpectedly exhibited lower proton conductivity than Ni-CP, which is non-porous and contains much less water content.

Lithium(I), Cesium(I), Barium(II) and Cadmium (II) [2-(2,6-dichlorophenylamino)phenyl]acetate (diclofenac) complexes and coordination polymers

Two new lithium complexes and three coordination polymers with cesium, barium, and cadmium having deprotonated diclofenac acid (HDFA) ligand are reported. All these non-ionic complexes or the coordination polymers were characterized by single crystal X-ray diffraction, IR and thermal studies. The lithium-diclofenac complexes, [Li(DFA)(H2O)3] and [Li(DFA)(H2O)2(DMF)] were respectively obtained from reaction carried out in aqueous ethanol or dimethylformamide as solvent. Each formed hydrogen bonded 2D-sheets, which were further assembled into 3D-layers by involving edge-on Cl-π interactions. The respective average particle sizes determined by dynamic light scattering of the respective lithium complexes were 648.3 nm and 588.8 nm. The average particle size of the tri-aquated complex dissolved in water was decreased upon addition of dimethylformamide. The cesium coordination polymer [Cs(DFA)(μ-H2O)2]n had two-dimensional sheets formed through dative bonds. The hydrophobic parts of the sheets were projecting outward and two alternative sheets were inter-linked by edge-on chlorine-π interactions (3.391 Å) to provide 3-D supramolecular layered structure. One dimensional barium coordination polymer [Ba(DFA)2(H2O)4]n and a cadmium coordination polymer [{Cd(DMF)4}2+{Cd(DFA)4}2−]n having linear-chain structure were reported. The linear chain of the cadmium coordination polymer was comprised of the coordinatively linked assembly of complex cation [Cd(DMF)4]2+ with anion [Cd(DFA)4]2− located at alternative positions by side-on carboxylate bridges.

2D Cadmium(II) Coordination Polymer Based on 2,5-Furandicarboxylate and 1,4-Bis(1H-imidazol-1-yl)butane Linkers: Synthesis, Characterization and DFT Studies

AbstractAs a result of hydrothermal synthesis of 2,5-furandicarboxylate (fdc2−), Cd(II) ion and bis(imidazole) derivative 1,4-bis(1H-imidazole-1-yl)butane (bib) ligand, a novel two-dimensional Cd(II) coordination polymer {[Cd(µ-fdc)(H2O)(µ-bib)]·H2O}n (1) was synthesized. According to the results of single crystal X-ray diffraction analysis, the complex was crystallized in the monoclinic system and in the P21/n space group. In addition, the thermal, luminescence and optical properties of the complex were investigated. The complex emits a maximum at 509 nm and also shows semi-conductor properties according to the solid-state UV–Vis diffuse reflection spectra results. To determine chemical structure, vibrational properties and some chemical properties of complex, theoretical calculations were carried out. All theoretical computations were performed using the DFT method at the B3LYP/LanL2DZ level of theory. The obtained experimental results were in good agreement with theoretical results. To calculate HOMO–LUMO energy values, which provided insights into the material's electronic properties, DFT calculations were used. Detailed information about the local and global chemical activity, as well as the electrophilic and nucleophilic nature of the complex, were also obtained.

PH-dependent synthesis, characterization, crystal structures, and acetone sensing properties of two new 1D ladder-like cadmium(II) coordination polymers based on 4,4′-bipyridine and benzoate ligands

Two new 1D ladder-like cadmium(II) coordination polymers, [Cd(4,4′-bipy)(benz)(NO3)]n (1) and [Cd3(4,4′-bipy)4(benz)6(H2O)2]n (2) (4,4′-bipy = 4,4′-bipyridine and benzH = benzoic acid) have been synthesized by slow evaporation method with different pH of 5.0 and 7.0 and fully characterized. Interestingly, the pH-dependent synthesis provides different molecular topologies, 1D ladder-like chain and net for compounds 1 and 2, respectively. The photoluminescent and sensing properties of both compounds for small organic molecules have been investigated. The results show that both compounds present a selective response to acetone in acetonitrile media through luminescence quenching with LOD of acetone concentration of 0.047 v/v% and 0.091 v/v% for compounds 1 and 2, respectively.

Synthesis and crystal structure of a cadmium(II) coordination polymer based on 4,4′-(1H-1,2,4-triazole-3,5-diyl)dibenzoate

The asymmetric unit of the title compound, catena-poly[[[aquabis(pyridine-κN)cadmium(II)]-μ2-4,4′-(1H-1,2,4-triazole-3,5-diyl)dibenzoato-κ4 O,O′:O′′,O′′′] 4.5-hydrate], {[Cd(C16H9N3O4)(C5H5N)2(H2O)]·4.5H2O} n or {[Cd(bct)(py)2(H2O)]·4.5H2O} n (I), consists of a Cd2+ cation coordinated to one bct2– carboxylate dianion, two molecules of pyridine and a water molecule as well as four and a half water molecules of crystallization. The metal ion in I possesses a pentagonal–bipyramidal environment with the four O atoms of the two bidentately coordinated carboxylate groups and the N atom of a pyridine molecule forming the O4N equatorial plane, while the N atom of another pyridine ligand and the O atom of the water molecule occupy the axial positions. The bct2– bridging ligand connects two metal ions via its carboxylic groups, resulting in the formation of a parallel linear polymeric chain running along the [1\overline{1}1] direction. The coordinated water molecule of one chain forms a strong O—H...O hydrogen bond with the carboxylate O atom of a neighboring chain, leading to the formation of double chains with a closest distance of 5.425 (7) Å between the cadmium ions belonging to different chains. Aromatic π–π stacking interactions between the benzene fragments of the anions as well as between the coordinated pyridine molecules belonging to different chains results in the formation of sheets oriented parallel to the (\overline{1}01) plane. As a result of hydrogen-bonding interactions involving the water molecules of crystallization, the sheets are joined together in a three-dimensional network.

Structural diversity of cadmium coordination polymers based on an extended anilate-type ligand

The extended anilate ligand is an excellent platform for designing MOFs with diverse structures and topologies.

Fabrication, Crystal Structures, Catalytic, and Anti-Wear Performance of 3D Zinc(II) and Cadmium(II) Coordination Polymers Based on an Ether-Bridged Tetracarboxylate Ligand

Two 3D Zn(II) and Cd(II) coordination polymers, [Zn2(µ4-dppa)(µ-dpe)(µ-H2O)]n·nH2O (1) and [Cd2(µ8-dppa)(µ-dpe)(H2O)]n (2), have been constructed hydrothermally using 4-(3,5-dicarboxyphenoxy)phthalic acid (H4dppa), 1,2-di(4-pyridyl)ethylene (dpe), and zinc or cadmium chlorides. Both compounds feature 3D network structures. Their structure and topology, thermal stability, catalytic, and anti-wear properties were investigated. Particularly, excellent catalytic performance was displayed by zinc(II)-polymer 1 in the Knoevenagel condensation reaction at room temperature.

Metal-Organic Coordination Polymers of Cadmium Based on Anilate Ligands

Metal-Organic Coordination Polymers of Cadmium Based on Anilate Ligands

Assembly of two luminescent cadmium(II) 4,4'-phosphini Co-dibenzoate coordination polymers

Two new cadmium(II) coordination polymers [Cd(HL)(H2O)]·1.5H2O (1) and [Cd(HL)(4-bpmp)0.5]·2H2O (2) (H3L = 4,4'-phosphinicobis-dibenzoic acid, and 4-bpmp = N,N'-bis(4-pyridylmethyl)piperazine) have been synthesized by self-assembly of CdCl2 with 4,4'-phosphinicobis-dibenzoate, and N,N'-bis(4-pyridylmethyl)piperazine through solvothermal/hydrothermal method. Their structures were confirmed by X-ray single crystal diffraction, infrared spectrometer (IR), and powder X-ray diffraction (PXRD) and TGA techniques. Both compounds are in Pī space group and exhibited a 2D networks constructed from dinuclear [Cd2(POO)2] or paddle-wheel [Cd2(COO)2(POO)2] units, respectively. In 2, the Cd2+ is five-coordinated and shows a rare tetragonal pyramidal geometry. At room temperature, the compounds exhibit moderately intense blue and green fluorescence emission with peaks at 381 nm and 509 nm, respectively.
 KEY WORDS: Cadmium(II) compounds, Photoluminescence, Carboxyphosphinate ligand
 Bull. Chem. Soc. Ethiop. 2024, 38(1), 85-98. DOI: https://dx.doi.org/10.4314/bcse.v38i1.7

Synthesis and Fluorescence Sensing for Nitro Explosives and Pesticides of Two Cd-Coordination Polymers.

Two cadmium coordination polymers (CPs), {[Cd(zgt)(2,2'-bipy)(H2O)]·H2O}n (1) and {[Cd(zgt)(BPP)(H2O)]·H2O}n (2) (H2zgt = 5-methoxyresorcinic acid, 2,2'-bipy = 2,2'-bipyridine, and BPP = 1,3-bis(4-pyridyl)propane), were prepared by the hydrothermal method. The structures of CPs 1-2 were characterized by IR, TGA, X-ray powder diffraction, and elemental analysis. The single-crystal structure analysis shows that CP 1 is a typical 1D chain structure and CP 2 belongs to a 2D layered structure. Based on the excellent luminescence properties of CP 1 and 2, fluorescence sensing experiments were carried out for explosives and pesticides. The results of the explosion sensing experiment showed that CP 1 and 2 had an excellent fluorescence quenching effect on PNBA (p-nitrobenzoic acid) and TNP (2,4,6-trinitrophenol), respectively, and the detection limits were 3.28 and 11.4 nM, respectively. Interestingly, both CP 1 and 2 showed good fluorescence quenching against the pesticide fluridine (Flu), and CP 1 had a lower detection limit and was more sensitive. In addition, the fluorescence quenching mechanism was discussed in detail by the UV absorption spectrum and density functional theory. In order to explore its practical application, the content of Flu in water samples was detected by a labeling recovery method.

C–H Azidation System Induced by Visible Light from Triboelectric Nanogenerators Based on a Cadmium Coordination Polymer

C–H Azidation System Induced by Visible Light from Triboelectric Nanogenerators Based on a Cadmium Coordination Polymer

Cadmium(II) coordination polymers based on 3,3′-azobis(pyridine) and some aliphatic dicarboxylates: Hydrothermal synthesis, crystal structures, thermal stabilities and photoluminescence

Three new Cd(II) coordination polymers (CPs), namely, [Cd2(µ-phsuc)2(µ-abpy)2(H2O)2]n (1), {[Cd(μ3-glu)(μ-abpy)]⋅3H2O}n (2) and {[Cd(μ-dmglu)(μ-abpy)(H2O)]⋅H2O}n (3), were synthesized by hydrothermally from 3,3′-azobis(pyridine) (abpy) using three different aliphatic dicarboxylic acids [phenyl succinic acid (phsucH2), glutaric acid (gluH2) and 3,3′-dimethyl glutaric acid (dmgluH2)]. The structures of 1–3 were characterized by elemental analysis, infrared spectroscopy (IR), single crystal X-ray and powder X-ray diffraction (PXRD) techniques. X-ray diffraction studies have revealed that 1–3 crystallize in the monoclinic system, P21/n space group (1) and C2/c space group (2, 3). 1 and 2 show 3D structure, whereas 3 exhibits an interesting 2-fold interpenetrating 2D structure. The thermal stabilities of the CPs were studied by thermal analysis (TG/DTA) techniques. In addition, the photoluminescence properties of the CPs have been investigated.

Topological control through the solvent effect in two-dimensional cadmium coordination polymers

Two new solvent-induced cadmium (II) coordination polymers, {[CdL1.5(NO3)2](CH3CN)}n (1) and [CdL(NO3)2(H2O)]n (2) were successfully synthesized from the same initial materials Cd(NO3)2.4H2O and 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene (L) in EtOH/CH3CN and CH3CN solvent systems, respectively. These coordination polymers were structurally characterized by single-crystal X-ray diffraction analysis and further identified by infrared spectra (FTIR) and powder X-ray diffraction (PXRD). The influence of the solvent system can be observed by a significant change in the topological features. As controlled by solvent, compound 1 shows a 2D coordination polymer that can be simplified as a (6,3) net, while compound 2 is two-dimensional (4,4) coordination network. Our results provide interesting insights into solvent effects on the topological control in construction of non-interpenetrated coordination polymers. Hirshfeld surface analysis of the structures 1 and 2 is used to investigate the percentage of participation of intermolecular interactions in the crystal packing of compounds 1 and 2.

Structure and photochromic properties of two cadmium coordination polymers derived from viologen ligands

AbstractTwo novel 1D Cd‐based coordination polymers (CPs) {[Cd(MQ)(HBTC)(H2O)2] ⋅ (H2BTC) ⋅ 4H2O}n (1) and {[Cd(AQ)(HBTC)(H2O)Br] ⋅ 2H2O}n (2) have been prepared in the reaction of Cd2+ with different viologen ligands such as 1‐methyl‐4,4′‐bipyridinium bromide (MQBr) or 1‐amyl‐4,4′‐bipyridinium bromide (AQBr) in the presence of 1,3,5‐benzenetricarboxylic acid (H3BTC). The Cd2+ ions are bridged by HBTC2− anions to take shape a 1D configuration for two CPs. Additionally, 1 and 2 both show photochromism due to the photoinduced electron transfer (ET) from electron‐rich O atoms to electron‐deficient viologen moieties. Compared with 2, compound 1 has a rapid photoresponsive rate. The different photochromic behaviors have been discussed adequately.

Anion-induced structural diversity in cadmium coordination polymers of 4-aminobenzonitrile: a structural and DFT study

Using 4-aminobenzonitrile and different anions, five cadmium CPs, [Cd(4-ABN)I2]n (1), [Cd(4-ABN)Br2]n (2), [Cd(4-ABN)2(NO3)2]n (3), [Cd(4-ABN)2(OAc)2]n (4) and {[Cd(4-ABN)2(H2O)2](ClO4)2}n (5), are synthesized and structurally characterized.

Two New Coordination Polymers of Cadmium with Bridging Thiocyanate Ligands: Composition and Structure

Two New Coordination Polymers of Cadmium with Bridging Thiocyanate Ligands: Composition and Structure

Structural Characterization of Zinc(II) and Cadmium(II) Coordination Polymers Composed of Bis(4-(1H-imidazol-1-yl)phenyl)methanone and 1,3-Adamantanedicarboxylate Ligands

Structural Characterization of Zinc(II) and Cadmium(II) Coordination Polymers Composed of Bis(4-(1H-imidazol-1-yl)phenyl)methanone and 1,3-Adamantanedicarboxylate Ligands

Solvothermal synthesis and crystal structures of two new cadmium coordination polymers containing polynitrile ligands

Two new coordination polymers of cadmium-containing polynitrile ligands have been synthesized using sovothermal methods. In both poly[trans,trans,trans-bis(μ-dicyanamido-κ2 N 1:N 3)bis(2-methylbenzimidazole-κN)cadmium(II)], [Cd(C2N3)2(C8H8N2)2] n , (I), and poly[trans,trans,trans-bis(2-methylbenzimidazole-κN)bis(μ-tricyanomethanido-κ2 N:N′)cadmium(II)], [Cd(C4N3)2(C8H8N2)2] n , (II), the Cd atom lies on a centre of inversion, in space groups P21/n and P21/c, respectively. In each polymer, each anionic ligand acts as a bridge between two metal centres, forming sheets of 24-membered rings, and in each structure a single N—H...N hydrogen bond links the polymer sheets to form a three-dimensional framework structure. Comparisons are made with the structures of some related complexes.