Three-dimensional Coordination Polymer Research Articles

Functional Three-Dimensional Ce-Based Coordination Polymer: Synthesis, Structure, and Selective Sensing of Lysine and Arginine Based on the Luminescence Turn-On Effect

Functional Three-Dimensional Ce-Based Coordination Polymer: Synthesis, Structure, and Selective Sensing of Lysine and Arginine Based on the Luminescence Turn-On Effect

Luminescent Coordination Polymers with Mixed Carboxylate and Triazole Ligands for Rapid Detection of Chloroprene Metabolite

Chloroprene is a monomer widely used in the production of neoprene, and 1-hydroxy-2-butanone (1H2B) is one of the metabolites of chloroprene in urine, which can place a significant impact on human health by disrupting the normal structure and function of DNA. Herein, a three-dimensional Zn-based coordination polymer (1) and a two-dimensional Cd-based coordination polymer (2) were synthesized with mixed ligands of 2,5-furandicarboxylic acid (H2FDA) and 1,2,4-triazole (Htrz) and fully characterized. 2 exhibits excellent stability and superior sensing performance for 1H2B with fast response within 15 s, good recyclability and a detection limit of 9.24 μM. In addition, 2 demonstrates good selectivity in presence of main coexisting compounds in urine. In-depth investigations of the sensing mechanism revealed that the luminescence sensing is based on the competitive absorption and photoelectron transfer processes.

Two 3D Zn(II)/Co(II)-CPs as fluorescent sensors for turn-on and red-shift sensing of tryptophan and norfloxacin

Two three-dimensional (3D) coordination polymers (CPs), namely {[M(seb)(bbimb)]·3H2O}n (M = Zn for 1; Co for 2), were obtained via hydrothermal method using sebacic acid (H2seb) mixed with 1,4-bis(benzoimidazol-1-yl)butane (bbimb). The structures of 1 and 2 both display as 3D frameworks with a 5-fold interpenetrating dia topology. CPs 1 and 2 both exhibit excellent luminescent properties and good water stability. Fluorescence sensing experiments demonstrate that 1 and 2 both can selectively detect tryptophan (Trp) and norfloxacin (Nor) in aqueous solution through turn-on and red-shift effect with remarkable anti-interference ability and low detection limits. The limits of detection (LOD) toward Trp-and Nor are 0.07 μM, 0.08 μM for 1 and 0.41 μM, 0.11 μM for 2. In addition, theoretical calculations and different detection methods were utilized to thoroughly investigate the potential sensing mechanisms for Trp-and Nor. Importantly, 1 and 2 represent two rare examples for sensing both Trp-and Nor via turn-on and red-shift effects. The fluoresence test films of 1 and 2 were prepared which can detect Trp-and Nor quickly with naked eye.

Synthesis, Characterization, Investigation of Catalytic and Thermal Properties of Three-Dimensional and Layered Copper Organodiphosphonate Coordination Polymer

Bu çalışmada, (1,4-fenilenbis(metilen))bis(fosfonik asit) ligandı (H4L) ve katmanlı yapıya sahip bakır organodifosfonat polimeri, [Cu2(C8H8O6P2)(H2O)2]n (1), sentezlenmiştir. Sentezlenen bileşiklerin yapıları çeşitli spektroskopik ve analitik yöntemler kullanılarak karakterize edilmiştir. Tek kristal X-ray analizi sonucunda 1 nolu bileşiğin üç boyutlu ve sütunlu tabaka yapısında organik/inorganik katmanlardan oluştuğu gözlenmiştir. Monoklinik kristal sistemi ve P21/c uzay grubunda olan bileşik 1'in hücre parametreleri a = 10.8142(9) Å, b = 7.5839(6) Å, c = 7.3991(6) Å, V = 606.26(9) Å3 ve Z= 4'tür. Polimer zinciri içinde her bir bakır atomu toplam beş koordinasyona sahip olup kısmen bozulmuş kare piramit geometridedir. 1 polimerinin heterojen katalitik aktivitesi ve termal özellikleri incelenmiştir. TG analizi sonuncunda katalizörün 200 ᵒC sıcaklığa kadar termal kararlılığa sahip olduğu gözlenmiştir. TBHP kullanarak 60 ᵒC sıcaklıkta ve 12 saat sonunda %92.37 timol dönüşümü meydana gelmiştir.

A cobalt-coordination polymer as a highly selective and sensitive luminescent sensor for detecting 2,4,6-trinitrophenol

In this paper, a new three-dimensional network coordination polymer {[Co(TPTC)(HBPDPE)2·2H2O]·3H2O} n [[[(1:1′:4′,1″-terphenyl)-3,3″,5,5″-tetracarboxylic cobalt (II)] dipyridine dihydrate] trihydrate] (Complex 1) was generated under solvothermal synthesis by rigid conjugated ligand H4TPTC ([1:1′:4′,1″-terphengl]-3,3″,5,5″-tetracarboxylic), V-shaped BPDPE (4,4′-bis (pyridyl) diphenyl ether) and Co(II) ion. In complex 1, the neighboring Co(II) ions are linked by deprotonated TPTC4- to achieve a 1D zigzag chain [Co(TPTC)(HBPDPE)2] n , then the adjacent [Co(TPTC)(HBPDPE)2] n chains linked each other by various H-bondings to extend the structure from 1D chain to 3D network. Complex 1 has excellent fluorescence sensing performance and exhibits high sensitivity and selectivity for detecting 2,4,6-trinitrophenol (TNP), the quenching constant K sv is up to 2.08 × 105 M−1 along with the correlation coefficient R 2 of 0.993. Furthermore, the quench mechanisms of this Co-MOF as a sensor to detect nitro- aromatic explosives were studied as well.

Crystal-to-crystal investigations of highly thermally stable three-dimensional coordination polymer based on sodium(I) ions and 4,4’-stilbenedicarboxylic acid

The new three-dimensional coordination polymer termed {[Na<sub>2</sub>SDC(H<sub>2</sub>O)]}<sub>n</sub> (SDC<sup>2-</sup>= C<sub>16</sub>H<sub>10</sub>O<sub>4</sub><sup>2-</sup>) has been synthesized using workstation Easymax 102 while controlling the conditions and monitoring in-situ reagents. The metal complex was obtained in the reaction of sodium hydroxide with a suspension of 4,4’-stilbenedicarboxylic acid in aqueous medium. The compound was characterized by elemental analysis, single crystal, and powder X-ray diffraction methods, ATR-FTIR spectroscopy, SEM and optical microscopy, TG-DSC and TG-FTIR thermal analysis in air and nitrogen atmosphere. In the crystal structure of {[Na<sub>2</sub>SDC(H<sub>2</sub>O)]}<sub>n</sub> appears penta- and hexacoordinated sodium atoms joined by octa- and decadentate SDC2- linkers. Aqua ligand acts as bridge between Na1 and Na2 atoms. The as-synthesized sodium complex is thermally stable up to 86<sup>o</sup>C whereas its dehydrated form has extreme stability up to 491<sup>o</sup>C. Removal of water molecule leads to the crystal-to-crystal transformation yielded changes in coordination modes of COO groups. Reversibility of the hydration process in the studied complex was also examined.

A two-fold interpenetrated mixed-ligands acentric 3D coordination polymer Zn(OBA)(DIB)·0.5H2O: Topological analysis, fluorescent and second-order NLO properties

Second-order nonlinear optical (NLO) materials have important applications in the realms of photoelectronics and photonics whose microstructures need to be organized into a noncentrosymmetric (NCS) structure. In this work, a mixed-ligands three-dimensional (3D) noncentrosymmetric coordination polymer Zn(OBA)(DIB)·0.5H2O (1) was hydrothermally prepared from 4, 4′-oxydibenzoic acid (H2OBA), 1, 3-di(1H-imidazol-1-yl)benzene (DIB) and Zn(NO3)2·6H2O via spontaneous resolution approach, which crystallizes in a noncentrosymmetric space group Fdd2. Compound 1 was characterized by powder X-ray diffraction (XRD), thermogravimetric (TGA) and IR analyses. The structural analysis shows that 1 is a two-fold self-interpenetrated three-dimensional (3D) network material. Single crystal X-ray diffraction and the topological analysis manifests that the topological structure of 1 belongs to a cds topological net. The measurement of the fluorescent properties of 1 and the free DIB ligand show that the emission peak at 460 nm of 1 can be attributed to the charge transition from the п bond electron to the п anti-bond orbital of the DIB ligand. The second-harmonic generation (SHG) measurement shows that the second-order NLO effect of compound 1 is approximately equivalent to that of potassium dihydrogen phosphate (KDP). Compound 1 is high thermal stable and insoluble in water and common organic solvents, making it to be a potential candidate as a second-order NLO material.

A Series of Novel 3D Coordination Polymers Based on the Quinoline-2,4-dicarboxylate Building Block and Lanthanide(III) Ions-Temperature Dependence Investigations.

A series of novel 3D coordination polymers [Ln2(Qdca)3(H2O)x]·yH2O (x = 3 or 4, y = 0-4) assembled from selected lanthanide ions (Ln(III) = Nd, Eu, Tb, and Er) and a non-explored quinoline-2,4-dicarboxylate building block (Qdca2- = C11H5NO42-) were prepared under hydrothermal conditions at temperatures of 100, 120, and 150 °C. Generally, an increase in synthesis temperature resulted in structural transformations and the formation of more hydrated compounds. The metal complexes were characterized by elemental analysis, single-crystal and powder X-ray diffraction methods, thermal analysis (TG-DSC), ATR/FTIR, UV/Vis, and luminescence spectroscopy. The structural variety of three-dimensional coordination polymers can be ascribed to the temperature effect, which enforces the diversity of quinoline-2,4-dicarboxylate ligand denticity and conformation. The Qdca2- ligand only behaves as a bridging or bridging-chelating building block binding two to five metal centers with seven different coordination modes arising mainly from different carboxylate group coordination types. The presence of water molecules in the structures of complexes is crucial for their stability. The removal of both coordinated and non-coordinated water molecules leads to the disintegration and combustion of metal-organic frameworks to the appropriate lanthanide oxides. The luminescence features of complexes, quantum yield, and luminescent lifetimes were measured and analyzed. Only the Eu complexes show emission in the VIS region, whereas Nd and Er complexes emit in the NIR range. The luminescence properties of complexes were correlated with the crystal structures of the investigated complexes.

Blue-Emitting 2D- and 3D-Zinc Coordination Polymers Based on Schiff-Base Amino Acid Ligands

The solvothermal reaction of Zn(NO3)2·4H2O, 1-OH-2-naphthaldehyde, and 2-methylalanine (mAla) in MeOH leads to the formation of complex {[ZnL1]}2n (1) (H2L1 = the Schiff-base resulting from the reaction of 1-OH-2-naphthaldehyde and mAla) in good yields. The structure of the neutral species, as determined by single-crystal crystallography, describes a two-dimensional coordination polymer, with repeating {Zn2} units bridged by syn, anti-carboxylate groups of the Schiff-base ligands. Repeating the same reaction using glycine (gly) instead of mAla leads to the formation of complex {[ZnL2]·0.33MeOH}3n (2.0.33MeOH) (H2L2 = the Schiff-base resulting from the reaction of 1-OH-2-naphthaldehyde and gly), again in good yields. Complex 2 describes a three-dimensional coordination polymer based on {Zn2} building blocks, arranged by anti, anti-carboxylate groups in a 3D motif. Complexes 1 and 2 were found to strongly emit at ~435 nm (λexc = 317 nm) both in solution and solid state, with complex 2 displaying a slightly longer lifetime of τav = 2.45 ns vs. τav = 2.02 ns for 1.

Isobutene isomerization via metal-organic coordination polymer catalyst

One-dimensional, two-dimensional and three-dimensional Ni-containing metal-organic coordination polymer (1D-Ni, 2D-Ni and 3D-Ni MOCP) catalysts were solvothermally synthesized and used for isomerization of isobutene. These catalysts showed the same conversion of isobutene and selectivity for 2-butene as homogeneous catalysts. At the same time, 1D-Ni catalyst evacuated at 100 °C revealed the conversion of isobutene and selectivity to 2-butene were up to 89.2% and 100.0%, respectively. Moreover, the results demonstrated that the conversion of isobutene was different depending on metal coordination mode, dimension of coordination polymer, and the reaction pressure. In addition, The MOCP catalysts were relatively environmentally friendly, and easily recovered and recycled. Finally, the mechanism of metal hydride addition elimination was proposed.

A series of isostructural Ln-based coordination polymers: Crystal structure, luminescence sensing and color tuning

Compared with traditional detection methods, fluorescent sensors have many advantages in identifying metal ions. Herein, a new series of three-dimensional (3D) lanthanide coordination polymers (CPs) [Eu3(FDA)4(DMSO)2(NO3)(H2O)2]n (CP-1), [Tb3(FDA)4(DMSO)2(NO3)(H2O)2]n (CP-2) and [Eu3xTb3(1-x)(FDA)4(DMSO)2(NO3)(H2O)2]n (Eu/Tb-CP) based on 2,5-furandicarboxylic acid (H2FDA) were synthesized. Single-crystal X-ray diffraction indicated that both the CP-1 and CP-2 were isomorphic with a topology of {42.5}2{44.510.69.74.8} based on trinuclear second building units to form a 3D framework. Luminescence sensing experiments revealed that CP-1 has a good selection and recognition effect on Fe3+ (Ksv = 3.3 × 104 M−1, limit of detection (LOD) = 2.31 μM) and shows great potential as a luminescence sensor. Additionally, color tuning could be achieved by doped Eu3+ and Tb3+ into the reaction mixtures using the synergistic effect of their luminescent centers.

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This article refers to:RETRACTED ARTICLE: Two-/three-dimensional coordination polymers: structural characterization and treatment activity on ulcerative colitis by regulating inflammatory cytokines

A Series of Metal–Organic Frameworks with 2,2′-Bipyridyl Derivatives: Synthesis vs. Structure Relationships, Adsorption, and Magnetic Studies

Five new metal-organic frameworks based on Mn(II) and 2,2'-bithiophen-5,5'-dicarboxylate (btdc2-) with various chelating N-donor ligands (2,2'-bipyridyl = bpy; 5,5'-dimethyl-2,2'-bipyridyl = 5,5'-dmbpy; 4,4'-dimethyl-2,2'-bipyridyl = 4,4'-dmbpy) [Mn3(btdc)3(bpy)2]·4DMF, 1; [Mn3(btdc)3(5,5'-dmbpy)2]·5DMF, 2; [Mn(btdc)(4,4;-dmbpy)], 3; [Mn2(btdc)2(bpy)(dmf)]·0.5DMF, 4; [Mn2(btdc)2(5,5'-dmbpy)(dmf)]·DMF, 5 (dmf, DMF = N,N-dimethylformamide) have been synthesized, and their crystal structure has been established using single-crystal X-ray diffraction analysis (XRD). The chemical and phase purities of Compounds 1-3 have been confirmed via powder X-ray diffraction, thermogravimetric, and chemical analyses as well as IR spectroscopy. The influence of the bulkiness of the chelating N-donor ligand on the dimensionality and structure of the coordination polymer has been analyzed, and the decrease in the framework dimensionality, as well as the secondary building unit's nuclearity and connectivity, has been observed for bulkier ligands. For three-dimensional (3D) coordination polymer 1, the textural and gas adsorption properties have been studied, revealing noticeable ideal adsorbed solution theory (IAST) CO2/N2 and CO2/CO selectivity factors (31.0 at 273 K and 19.1 at 298 K and 25.7 at 273 K and 17.0 at 298 K, respectively, for the equimolar composition and the total pressure of 1 bar). Moreover, significant adsorption selectivity for binary C2-C1 hydrocarbons mixtures (33.4 and 24.9 for C2H6/CH4, 24.8 and 17.7 for C2H4/CH4, 29.3 and 19.1 for C2H2/CH4 at 273 K and 298 K, respectively, for the equimolar composition and the total pressure of 1 bar) has been observed, making it possible to separate on 1 natural, shale, and associated petroleum gas into valuable individual components. The ability of Compound 1 to separate benzene and cyclohexane in a vapor phase has also been analyzed based on the adsorption isotherms of individual components measured at 298 K. The preferable adsorption of C6H6 over C6H12 by 1 at high vapor pressures (VB/VCH = 1.36) can be explained by the existence of multiple van der Waals interactions between guest benzene molecules and the metal-organic host revealed by the XRD analysis of 1 immersed in pure benzene for several days (1≅2C6H6). Interestingly, at low vapor pressures, an inversed behavior of 1 with preferable adsorption of C6H12 over C6H6 (KCH/KB = 6.33) was observed; this is a very rare phenomenon. Moreover, magnetic properties (the temperature-dependent molar magnetic susceptibility, χp(T) and effective magnetic moments, μeff(T), as well as the field-dependent magnetization, M(H)) have been studied for Compounds 1-3, revealing paramagnetic behavior consistent with their crystal structure.

Coordination Chemistry of Polynitriles, Part XII—Serendipitous Synthesis of the Octacyanofulvalenediide Dianion and Study of Its Coordination Chemistry with K+ and Ag+

The reaction of diazotetracyanocyclopentadiene with copper powder in the presence of NEt4Cl yields, unexpectedly, besides the known NEt4[C5H(CN)4] (3), the NEt4 salt of octacyanofulvalenediide (NEt4)2[C10(CN)8] (5), which can be transformed via reaction with AgNO3 to the corresponding Ag+ salt (4), which in turn can be reacted with KCl to yield the corresponding K+ salt 6. The molecular and crystal structures of 4–6 could be determined, and show a significantly twisted aromatic dianion which uses all its nitrile groups for coordination to the metals; 4 and 6 form three-dimensional coordination polymers with fourfold coordinated Ag+ and eightfold coordinated K+ cations.

A Robust Strontium Coordination Polymer with Selective and Sensitive Fluorescence Sensing Ability for Fe3+ Ions.

Exploration of sensitive and selective fluorescence sensors towards toxic metal species is of great importance to solve metal pollution issues. In this work, a three-dimensional (3D) strontium coordination polymer of Sr2(tcbpe) (H4tcbpe = 1,1,2,2-tetrakis(4-(4-carboxy-phenyl)phenyl)ethene) has been synthesized and developed as a fluorescent sensor to Fe3+ ions. Sr2(tcbpe) shows a mechanochromic fluorescence with emission shifting from blue of the pristine to green after being ground. Notably, based on a fluorescence quenching mechanism, Sr2(tcbpe) displays a sensitive and selective fluorescent sensing behavior to Fe3+ ions with a detection limit of 0.14 mM. Moreover, Sr2(tcbpe) exhibits high tolerance to water in a wide pH range (pH = 3-13), demonstrating that Sr2(tcbpe) is a potential fluorescent sensor of Fe3+ in water.

Two-Dimensional and Three-Dimensional Coordination Polymers Based on Ln(III) and 2,5-Diiodoterephthalates: Structures and Luminescent Behavior

Five new coordination polymers based on Ln3+ and 2,5-diiodoterephthalates (2,5-I-bdc)— {[La2(2,5-I-bdc)3(DMF)4]}·2DMF (1) and {[Ln2(2,5-I-bdc)3(DMF)4]} (Ln = La (2), Nd (3), Sm (4) and Eu (5))—were prepared and characterized by single crystal and powder X-ray diffractometry. Luminescent behavior was examined (the highest quantum yield is 4.5%); thermal stability was examined using thermogravimetric analysis.

Controllable Structural Modulation: Assembling Variable Dimension Energetic Metal-Organic Frameworks via Free Protons.

Herein, we provide an efficient strategy for constructing three-dimensional (3D) energetic coordination polymers (ECPs), namely, metal-organic frameworks (EMOFs), avoiding solvent coordination without changing the organic ligands or metal nodes. Three ECPs with the same ligand and metal center, namely, two-dimensional (2D) layer ECP [Pb(HOBTT)(H2O)2]n (1), 3D solvent-free EMOFs [Pb(HOBTT)]n (2), and dense [Pb3(OBTT)2]n (3) (H3OBTT = 4,5-bis(1-hydroxytetrazol-5-yl)-2H-1,2,3-triazole), were rationally designed and synthesized via free protons. As expected, the theoretical density of 3 (4.080 g·cm-3) is greater than those of 2 (3.299 g·cm-3) and 1 (3.055 g·cm-3). Thermal stabilities indicate that their decomposition temperature exceeds 300 °C. Theoretical calculations show that the detonation performance of 3 is better than that of 1 and 2. The detonation performance of 1-3 was further proven by laser irradiation.

Structural diversity and luminescence properties of M(II) complexes based on 4-carboxyphenoxybutanoic acid and N-containing ligands

4-Carboxyphenoxybutanoic acid (H2cpob) and its monosodium salt (NaHcpob) are synthesized and characterized. The crystal structure of NaHcpob shows that the sodium atoms are connected by the carboxyl group of Hcpob−, forming a three-dimensional coordination polymer network. NaHcpob reacts with metal salts and N-containing ligands produced following complexes: [Co(cpob)(H2O)2]n1, [Zn(cpob)(phen)(H2O)]22, [Cd(cpob)(phen)]n3, [Mn(cpob)(phen)·4H2O]n4, and [Cd2(cpob)2(bimb)]n5 (phen ​= ​1,10-phenanthroline, bimb ​= ​1,4-bis(imidazole-1-ylmethyl)benzene). Single-crystal X-ray diffraction analysis showed that these complexes have different metal-organic frameworks, ranging from binuclear (2) to one-dimensional (3 and 4), two-dimensional (1), and three-dimensional (5) arrangements. When only H2cpob forms a complex with metal ions, the ligand connects the metal ions into a higher-dimensional structure. In contrast, the terminal ligand (phen) added as an auxiliary ligand forms a low-dimensional complex. And when the bridging auxiliary ligand (bimb) is added, the high-dimensional complex can still be formed. The flexible conformation of H2cpob and the different N-containing ligands may be responsible for the structural diversity of binary H2cpob metal complexes. These metal complexes also displayed many differences in their fluorescence properties in the solid state.

A new mixed-valence CuI/CuII three-dimensional coordination polymer constructed with an N,O-donor ligand generated via solvothermal synthesis: structural features and magnetic properties.

A new mixed-valence CuI/CuII three-dimensional coordination polymer, poly[[diaquabis[μ4-2-(pyrazin-2-yl)quinoline-4-carboxylato]dicopper(I)copper(II)] bis(tetrafluoridoborate)], {[Cu3(C14H8N3O2)2(H2O)2](BF4)2}n, was synthesized and characterized, with 2-(pyrazin-2-yl)quinoline-4-carboxylic acid being employed as a linker ligand. The ligand was isolated as its hydrochloride salt, 4-carboxy-2-(pyrazin-2-yl)quinolin-1-ium chloride dihydrate, C14H10N3O2+·Cl-·2H2O. The compounds show luminescence at 550 nm for the ligand and at 565 nm for the polymer at 297 K. The ligand structure was rationalized by means of quantum-chemical calculations, which led to a similar conformation to that determined from X-ray diffraction studies.

Self-assembled three-dimensional coordination polymer with ligand-unsupported Ag–Ag bonds based on tetrazole-1-acetic ligand: Synthesis, structure, and properties

A new compound, [Ag2(tza)(NO3)]n(1), was obtained by reactions of 1H-Tetrazole-1-acetic (Htza) with AgNO3, and characterized by elemental analysis, infrared spectroscopy, and single crystal X-ray diffraction, respectively. The X-ray diffraction analysis reveals that compound 1 is three-dimensional (3D) metal-organic framework constructed by double-layer architecture and the ligand-unsupported Ag–Ag bonds, and displays an unprecedented (3, 6)-connected topological network with 1D hexagon channels of two sizes. The 1D zigzag Ag-metallic chain built from ligand-supported Ag–Ag bonds is observed in 1. Furthermore, the photoluminescence of 1 has also been investigated, and the result exhibits blue photoluminescence in the solid state at room temperature, which shows that this complex may be a good candidate for photoactive material. According to the crystal structures, the TDDFT/6-31G(d) approach was applied to study the photoluminescence emission of 1, and the calculated results are in good agreement with the experimental results.