1D Coordination Polymer Research Articles

Carboxylate bridging Cd(II)-based 1D coordination polymer: Structure, fabrication of Schottky device and selective sorption of Bromocresol Green

Phenyl-1,3-diacetate (1,3-PDAt) bridging Cd(II)-based 1D coordination polymer {[Cd(1,3-PDAt)(phen)]⋅(MeOH)⋅(H2O)0.5}n, (CP) where 1,10-phenanthroline (phen) serves as chelating ligand has been structurally confirmed by Single Crystal X-Ray Diffraction measurements along with other spectral data. The thermal treatment releases MeOH at ∼90 °C and the final product ends at CdO. The Tauc’s plot evaluates the band gap, 3.87 eV (calculated value, 3.76 eV) using absorption spectral data which marks the semiconducting nature of the material. This has motivated us to fabricate Schottky Diode device and the measured conductance is 8.87 × 10−6 S/m in the dark. Interestingly, 1D CP shows selective and specific sorption of Bromocresol Green (BG) out of four common dyes (Methylene blue, Methyl orange, Rhodamine B, and Bromocresol Green (BG)). Besides, the sorbed BG in the CP is leached out on treating with water and the CP has been re-used for further sorption studies. Thus, the CP is economically recycled which is the first principle of Sustainable Development Goals.

In situ TEM Pyrolysis of Conductive 2D Coordination Polymers for Improved Application as Solid Acid Fuel Cell Electrode Materials

In situ TEM Pyrolysis of Conductive 2D Coordination Polymers for Improved Application as Solid Acid Fuel Cell Electrode Materials

Lead(II) complex with methoxy-substituted beta-diketonate − structure, thermal behavior and unexpected thermolysis byproduct

New complex of lead(II) with beta-diketonate ligand PbL2 is described, where L=CH3COCHCOC(OCH3)(CH3)2, 5-methoxy-5-methylhexan-2,4-dionate). Crystal structure of the compound has been determined and its thermal properties have been studied. Chains of 1D coordination polymers form crystals of the complex, where the molecules are connected through the chelate-bridging oxygen atoms, methoxy groups remain free and form hydrogen bonds between the chains. PbL2 sublimates at 120 °C under reduced pressure (P=10−2 Torr) with partial decomposition. When heated in the condensed phase the complex decomposes with the formation of lead(II) oxide and evolution of a pyran derivative into gas phase. The mechanism of lead(II) complex thermolysis in support of the condensation of two ligands is discussed. A new organic product was identified by 13C and 1H NMR, IR and PL spectroscopy and mass spectrometry; the crystal structure of the product was determined.

From 0D-complex to 3D-MOF: changing the antimicrobial activity of zinc(II) via reaction with aminocinnamic acids.

Combining zinc nitrate with 3- and/or 4- aminocinnamic acid (3-ACA and 4-ACA, respectively) leads to the formation of the 0D complex [Zn(4-AC)2(H2O)2], the 1D coordination polymer [Zn(3-AC)(4-AC)], and the 2D and 3D MOFs [Zn(3-AC)2]∙2H2O and [Zn(4-AC)2]∙H2O, respectively. These compounds result from the deprotonation of the acid molecules, with the resulting 3- and 4-aminocinnamate anions serving as bidentate terminal or bridging ligands. All solids were fully characterized via single crystal and powder X-ray diffraction and thermal techniques. Given the mild antimicrobial properties of cinnamic acid derivatives and the antibacterial nature of the metal cation, these compounds were assessed and demonstrated very good planktonic cell killing as well as inhibition of biofilm growth against Pseudomonas aeruginosa, Escherichia coli, and Staphylococcus aureus.

New 1D Cd(II) coordination polymer based on L‒arginine ligand; Synthesis, X−ray structure, Hirshfeld analysis, DFT studies, and biological activity

The structural aspects of the newly synthesized 1D coordination polymer, [Cd(μ–L–Arg)(OSO3)(H2O)2]n with L−arginine (L−Arg) are presented. The Cd(II) is hepta−coordinated with one L‒Arg as a bridged bidentate ligand in addition to two water molecules and one sulphate group where both are monodentate ligands. The expansion of the coordination polymer along a–direction is occurred via two extra Cd–O bonds with the carboxylate group from another L−Arg in a neighboring complex unit. The significant interactions that controlled the molecular packing are O···H (52.8%) and H···H (32.2%) based on Hirshfeld topology analysis. The 1D polymeric structure of the Cd(II) is confirmed by the presence of obvious red spots in dnorm map related to the Cd−O coordinate bonds with the neighbouring molecule. The AIM investigation revealed that the Cd–O and Cd–N bonds have low covalent characters. The charge of Cd(II) is changed to 1.374 e as a consequence of complexation with the ligand groups. The orbital-orbital interactions included in the Cd–N and Cd–O bonds are analyzed using NBO calculations. The anticancer activity of the studied complex and L−Arg were screened versus human colorectal cell line (HCT−116). The results show that, the Cd(II) complex has better activity towards the tested cell line (IC50 = 166.15 ± 6.95 µg/mL) than its free ligand (IC50 = 224.42 ± 8.34 µg/mL). Also, the complex exhibits somewhat higher antibacterial activity compared with L‒Arg.

2D Coordination Polymers of Zn(II) with Diethylmalonic Acid Dianions and 4,4'-bipyridine: Synthesis and Structure

2D Coordination Polymers of Zn(II) with Diethylmalonic Acid Dianions and 4,4'-bipyridine: Synthesis and Structure

Semiconducting Copper(I) Iodide 2D-Coordination Polymers for Efficient Sunlight-Driven Photocatalysis in Dye Degradation

Semiconducting Copper(I) Iodide 2D-Coordination Polymers for Efficient Sunlight-Driven Photocatalysis in Dye Degradation

Bispidine Based Hg(II) 1D Coordination Polymers of Helical Topology: Stability, Selective Adsorption and 1D to 2D Dimensionality Change Via SC-to-SC Transformation.

Bispidine based Hg(II) coordination polymers of helical topology CP-MeOH and CP-EtOH are almost isostructural (they mainly differ for the solvent included in their lattice and by a small % in unit cell parameters) but they differ for everything else: i) their intrinsic stability, ii) their ability to adsorb solvents upon prior evacuation, iii) their accessible structural transformations. In particular, one of the two starting materials, once evacuated, is capable to adsorb methanol from atmospheres containing binary and ternary mixtures of volatile organic compounds (MeOH, CHCl3 and EtOH) under ambient conditions (25 °C, 1 atm) and with a marked selectivity. The other one is not, but undergoes a 1D to 2D dimensionality change which can be monitored in situ by SC-XRD through a SC-to-SC process.

Bimetallic Ba(II)-Cr(III) and trimetallic Ba(II)-Ln(III)-Cr(III) (Ln(III) = Gd, Tb, Dy, Ho, Er, Yb, Y) coordination polymers formed by Cr(III)-containing building blocks with cyclopropane-1,1-dicarboxylate anions

The reaction of chromium(III) nitrate with Ba(cpdc) (H2cpdc = cyclopropane-1,1-dicarboxylic acid) in a ratio of 1:3 yielded a 1D coordination polymer {[Ba2Cr2(OH)2(cpdc)4(H2O)8]·5H2O}n (1) formed by binuclear units [Cr2(OH)2(cpdc)4]4− and a 3D polymer [Ba2Cr(cpdc)3(NO3)(H2O)6]n (2) constructed from tris-chelate blocks [Cr(cpdc)3]3−. The addition of rare-earth metal nitrates (Cr:Ln = 1:2) in this reaction led to the formation of a series of trimetallic 3D coordination polymers {[Ba3Ln2Cr4(cpdc)12(H2O)24]·8H2O}n (3Ln, Ln = Gd, Tb, Dy, Ho, Er, Yb, Y), in whose structures tris-chelate fragments [Cr(cpdc)3]3− are bound in layers by Ln3+ ions and, further, in a framework due to the coordination of Ba2+ ions. The crystal structures of 1, 2, and 3Gd were determined by single-crystal X-ray diffraction (XRD), and isostructurality of all the compounds in the series 3Ln was proved by powder X-ray diffraction (PXRD). DC-magnetic susceptibility measurements revealed weak ferromagnetic exchange interactions between Cr3+ ions in compound 1 (J = +0.74 cm−1). According to ac-magnetic susceptibility measurements, complexes 3Er and 3Y exhibit field-induced slow relaxation of magnetization. According to the data of simultaneous thermal analysis (STA) and differential scanning calorimetry (DSC) performed under Ar atmosphere, dehydration of the compounds obtained takes place in one (for 1 and 3Gd) or three stages (for 2). The initial temperature of the organic part degradation process decreases when moving from compound 1 containing dimerized bis-chelate fragments [Cr2(OH)2(cpdc)4]4− (330 °C) to compounds 2 (276 °C) and 3Gd (261 °C) based on tris-chelate units [Cr(cpdc)3]3−.

Two Three-Dimensional LnIII Coordination Polymers Exhibiting Luminescent Sensing and a Magnetocaloric Effect.

Two lanthanide 3D coordination polymers [Ln2(L)4Cl2(H2O)4]n (Ln = Eu (1), Gd (2)) with quinoline-2-carboxylic acid (HL) as the ligand were successfully synthesized and characterized. Complex 1 exhibits a highly sensitive and selective luminescent response to 2,6-dipicolinic acid (DPA) in tap water and is virtually unaffected by interferences such as amino acids, aromatic carboxylic acids, and ions. With the addition of DPA, the luminescence intensity of complex 1 decreases rapidly to the naked eye. The detection limit of 1 toward DPA is 3.36 μM, which is much less than the infectious dose (60 μM) of the anthrax spores, indicating the high sensitivity of 1 to DPA. This study offers a basis for employing lanthanide complexes in real sample analysis, enabling direct and efficient detection of DPA with high sensitivity and specificity. Additionally, it is noteworthy that at a magnetic field strength of 7 T and a temperature of 3 K, the maximum entropy change for complex 2 attains a value of 23.56 J kg-1 K-1.

A polymeric copper complex based on a pyrazole derivative: Synthesis, spectroscopic, X‐ray, and biological activity studies

A novel 1D coordination polymeric copper complex based on 4‐(4′‐nitrophenylhydrazono)‐5‐trifluoromethyl‐2,4‐dihydropyrazol‐3‐one was prepared and characterized spectroscopically and thermally and via X‐ray crystallographic investigation. The prepared copper‐based structure was proved to have a 1D coordination polymer. X‐ray studies showed that the polymeric copper complex was of octahedral geometry, the ligand acted as a bidentate ligand, and the nitro group attached to the ligand acted as a bridging group. The cytotoxic activities of the copper polymer were evaluated including against MCF‐7 cells (breast cancer cell line), HepG‐2 cells (hepatocellular carcinoma), and HCT‐116 cells (colon cancer cell line). The morphological alterations of the complex treated cells were investigated using an inverted microscope. The cell cycle and apoptosis were evaluated and reported. The copper polymer exhibited the best antitumor activity against HepG‐2 cells (35.22 ± 4.80 μM) while also causing a decline in the G2/M phase and a remarkable enhancement in the early apoptosis.

Monomeric and Polymeric Cyclopentadienyl Dysprosium Complexes Based on the Acenaphthene-1,2-diimine Ligand

The reaction of [(Dpp-bian)DyI(Dme)2] (Dpp-bian is 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene, Dme is CH3OCH2CH2OCH3) with Cp*K (Cp* is C5Me5) in toluene followed by crystallization from benzene affords crystals of the 1D coordination polymer [(Dpp-bian)DyIKCp*]n (I)•2.6C6H6 (26%) and crystals of the monomeric complex [(Dpp-bian)DyCp*(Dme)] (II)•1.5C6H6 (12%). The same reaction in 1,2-dimethoxyethane followed by crystallization from benzene makes it possible to isolate only complex II•1.5C6H6 in a yield of 48%. The synthesized compounds are characterized by IR and UV spectroscopy and elemental and thermogravimetric analyses. Their molecular structures are determined by XRD (CIF files CCDC nos. 2298407 (I) and 2298408 (II)).

Oligomer and Polymer: Self Assembly of [Cp*Fe(η5‐P5)] and Ag(I) Salts of Bulky Weakly Coordinating Anions

AbstractReactions between the five‐fold symmetric building block [Cp*Fe(η5‐P5)] (A) and Ag(I) salts containing bulky weakly coordinating anions [TEF] and [FAL] ([TEF]=[Al{OC(CF3)3}4]–, [FAl]=[FAl{OC6F10(C6F5)}3]–) are presented. While, in the presence of Ag[TEF], A leads to the formation of a hitherto condensed 1D coordination polymer [{Ag(η2:η1‐A)2}]n[TEF]n (1), a new finite tetranuclear Ag(I) complex [{Ag4(η1‐A)2(η2:η1‐A)4(η1:η1‐A)2}][FAL]4 (3) was obtained with an Ag(I) salt bearing the weakly coordinating anion [FAl] increased in size. Various coordination modes (η2:η1; η1:η1 and η1) of A were observed in the solid‐state structure of 3, reflecting the adaptive coordination behavior of A towards Ag(I) ions. Structural modifications of the 1D polymer (1) can be controlled by the addition of a limited amount of MeCN yielding the unwound heteroleptic 1D polymer [{Ag(MeCN)2}3(η1:η1:η1‐A)2]n[TEF]3n (2). Moreover, in the presence of MeCN, the finite oligomeric compound 3 can also be converted into a new heteroleptic 1D polymer [{Ag(MeCN)}4(η1:η1‐A)5(η2:η1‐A)2]n[FAL]4n (4). The solid‐state structure of 4 discloses the existence of a unique 1,1,2‐η2:η1 (π,σ) coordination of A along with 1,3‐η1:η1 (σ) and 1,2‐η1:η1 (σ) coordination modes, while 1,2,4‐η1:η1:η1 (σ) coordination modes of A were found in 2. As revealed by X‐ray crystallography, in all the cases, the cationic moieties are well separated from the weakly coordinating anions in the solid state.

1D-Coordination Polymer of Copper(I) thiocyanate complex with metronidazole: Synthesis, crystal structure, Hirshfeld surface analysis, PXRD, Spectroscopic properties, MEP, QTAIM, π(CN)···tetrel interaction, RDG, and thermal analysis

Within 24 h of slow evaporation of the solution containing CuCl2·2H2O, metronidazole, and NH4SCN, a red-like crystalline Cu(I) complex titled [Cu(SCN)(mnz)]n (1), [where mnz = metronidazole; SCN = thiocyanate], was synthesized. The presence of SCN− during the synthesis induces reduction of the Cu(II) to Cu(I) giving rise to novel 1D coordination polymer. The compound was characterized by single crystal X-ray diffraction, powdered X-ray diffraction, spectroscopic proprieties, and Hirshfeld surface analysis. [Cu(SCN)(mnz)]n crystallizes in the monoclinic space group P21/c. The complex possesses a 1D layer structure constructed by linking the staircase-like [CuSCN]n chains. Intermolecular interactions in the crystals investigation via Hirshfeld surface analysis reveals the major contribution is from O···H/H···O interaction (22.9 %), which is due to the presence of hydrogen bonds of the O − H···O type. The thermal properties were investigated using DTA-TGA and DSC. The study comprises the interpretation of non-covalent interactions through Quantum Theory of Atoms in Molecules (QTAIM), Natural Bond Orbital (NBO) analyses, and Reduced Density Gradient (RDG). The results show the role of interactions between SCN− and mnz through multiple connections involving the oxygen, nitrogen, and sulfur lone pairs and π-bonds for constructing the unit cell. The non-covalent arrangements include very weak hydrogen bonds that cooperatively stabilize the crystal. Along with SCN− bridging copper atoms, growth in the ab plane is favored by an uncommon π···π interaction between SCN− and the imidazole ring of mnz. In this interaction, the π(SN) and π(CN) orbitals perturb the imidazole π(CN) orbital with energies of 0.36 and 0.22 kcal/mol, respectively. In the c direction, a hydrogen bond between the hydroxyl group and CH- fragment from different mnz molecules assists structure stabilization. It is accompanied by a rarely observed π(CN)···tetrel interaction, wherein SCN− donates π-electron density to the antibonding σ(CH) orbital of the methyl carbon.

Dynamic Interchain Motion in 1D Tetrathiafulvalene-Based Coordination Polymers for Highly Sensitive Molecular Recognition.

The application of electrically conductive 1D coordination polymers (1D CPs) in nanoelectronic molecular recognition is theoretically promising yet rarely explored due to the challenges in their synthesis and optimization of electrical properties. In this regard, two tetrathiafulvalene-based 1D CPs, namely [Co(m-H2TTFTB)(DMF)2(H2O)]n (Co-m-TTFTB), and {[Ni(m-H2TTFTB)(CH3CH2OH)1.5(H2O)1.5]·(H2O)0.5}n (Ni-m-TTFTB) are successfully constructed. The shorter S···S contacts between the [M(solvent)3(m-H2TTFTB)]n chains contribute to a significant improvement in their electrical conductivities. The powder X-ray diffraction (PXRD) under different organic solvents reveals the flexible and dynamic structural characteristic of M-m-TTFTB, which, combined with the 1D morphology, lead to their excellent performance for sensitive detection of volatile organic compounds. Co-m-TTFTB achieves a limit of detection for ethanol vapor down to 0.5ppm, which is superior to the state-of-the-art chemiresistive sensors based on metal-organic frameworks or organic polymers at room temperature. In situ diffuse reflectance infrared Fourier transform spectroscopy, PXRD measurements and density functional theory calculations reveal the molecular insertion sensing mechanism and the corresponding structure-function relationship. This work expands the applicable scenario of 1D CPs and opens a new realm of 1D CP-based nanoelectronic sensors for highly sensitive room temperature gas detection.

A Zn(II)-based 1D Coordination Polymer with Adsorption Properties and Hirshfeld Surface Analysis

A Zn(II)-based 1D Coordination Polymer with Adsorption Properties and Hirshfeld Surface Analysis

Structural Regulation of Four New d10 Coordination Polymers and Their Fluorescent Detection Properties for Nitro Compounds in Water

Structural Regulation of Four New d10 Coordination Polymers and Their Fluorescent Detection Properties for Nitro Compounds in Water

Structural Diversity and Rare η1 Cu-C Interactions in CuI Complexes of 1,2,3-Triazole-Functionalized Bisphosphines.

This manuscript describes the synthesis of copper complexes of 1,2,3-triazolyl-phosphines: o-Ph2P(C6H4){1,2,3-N3CC6H5)C(PPh2)} (L1), (C6H5){1,2,3-N3C(C6H4(o-PPh2))-C(PPh2)} (L2), 3-Ph2P(C5H3N){1,2,3-N3C(C6H5)C(PPh2)} (L3), o-Ph2P(C6H4){1,2,3-N3C(C5H5N)C(PPh2)} (L4), and {(3,5-Ph2PC6H4-o)21,2,3-N3CCH} (L5). The reactions of L1-L3 with CuI salts afforded dimeric complexes having the general formula [Cu2(μ -X)2L2] (L = L1, X = Cl, Br and I: 1 - 3; L= L2, X = Cl, Br and I: 4- 6; L = L3; X = Cl, Br, and I: 7-9). The reaction of L4 with CuI in a 1:2 molar ratio afforded 1D-coordination polymer [{(CuI)2{o-Ph2P(C6H4){1,2,3-N3C(C5H5N)C(PPh2)}-μ-((k1-N)(k2-P,P))}}]n (10). The reaction of L5 with cuprous halides (CuX) (X = Br, I) yielded mononuclear complexes [CuX{(3,5-Ph2PC6H4-o)21,2,3-N3CCH}-κ2P,P] (X = Br, 12; I, 13). Crystal structures of complexes 12 and 13 showed close interactions between CuI and the triazole C7 carbon. These relatively short Cu···C7 separations may be due to the η1-C interaction (dπ-pπ bond) between the triazolic carbon atom (via pz orbital) and CuI or three-centered two-electron interaction between CuI and the triazolic C-H bond. The existence of the Cu···C interaction was further evinced by the QTAIM analysis in compounds 12 and 13.

Zinc-based 1D coordination polymer for selective luminescent detection of nitrofuran antibiotics at part-per-billion level

With the harm caused by the misuse of antibiotics, the problem of water pollution has attracted much attention. Besides, water resources are closely related to human health. Therefore, the development of efficient and rapid methods for the detection of antibiotics is an important and urgent task. Here, a series of isostructural metal–organic framework materials (SYUCT-M, M = Zn, Co) was synthesized, SYUCT-Zn demonstrated sensing properties for efficient detection of nitrofuran antibiotics (NFAs). The detection limits of nitrofurazone (NFZ), furazolidone (FZD) and nitrofurantoin (NFT) by SYUCT-Zn were 1.47 ppb, 1.73 ppb and 2.43 ppb, respectively. Meanwhile, a fast response time and anti-interference ability of SYUCT-Zn is outstanding for 12 antibiotics in 5 classes. Apart from the sensitivity and selectivity, SYUCT-Zn featured excellent stability in acidic, basic or organic solvent media. Recyclability of SYUCT-Zn sensor was established, which indicates its great potential as sensory material for antibiotics detection.

Comparison of Electrical Conductivity and Schottky Behavior of 4‐[2‐(9‐anthryl)vinyl]pyridine Based Two 1D Coordination Polymers of Zn(II) and Cd(II)

AbstractWith the increase in demand of electronic devices in the modern civilization, research in material science is being projected to grow in faster rate. In this facet, coordination polymer (CP) based electronic device is one of the promising candidates to the material researchers. Herein, two new Zn(II) and Cd(II) based one‐dimensional (1D) CPs, denoted as [Zn(4‐avp)2(5‐nip)] ⋅ (solvent)x (1) and [Cd(4‐avp)(5‐nip)(CH3OH)] (2) have been synthesized using relatively less explored highly conjugated polycyclic aromatic hydrocarbon (PAH) based monodentate ligand, 4‐[2‐(9‐anthryl)vinyl]pyridine (4‐avp) and bidentate linker 5‐nitroisophthalic acid (H25‐nip). In this instance, the CP 1 creates 1D chain polymer, while CP 2 is made up with 1D ladder polymer. It is interesting to note that both the CPs exhibit semiconducting nature and generate metal‐semiconductor (MS) junction Schottky barrier diodes (SBDs). However, Cd‐based CP 2 shows higher charge transport as compared to Zn‐CP 1, which could be due to stronger π⋅⋅⋅π contacts as well as larger size of Cd metal in CP 2. The experimental results are well corroborated with theoretical density of states (DOS) calculations.