Phosphonate Coordination Polymers Research Articles

Statement of Retraction: Two transition metal phosphonate coordination polymers: application and nursing values on corneal disease during soft contact lenses usage

Statement of Retraction: Two transition metal phosphonate coordination polymers: application and nursing values on corneal disease during soft contact lenses usage

Combined separation-assay method for uranium in environmental water using a polyethylene-supported phosphonate coordination polymer membrane

Combined separation-assay method for uranium in environmental water using a polyethylene-supported phosphonate coordination polymer membrane

Two transition metal phosphonate coordination polymers: Treatment activity on recurrent oral ulcers by enhancing the immune response of macrophage

Two transition metal phosphonate coordination polymers [Cu(H2L)(4,4′-bipy)0.5] (1， H4L is 4-F-C6H4CH2N(CH2PO3H2)2, 4,4′-bipy is 4,4′-bipyridine) and [Zn2(L)(4,4′-bipy)1.5]·5H2O (2) have been produced through hydrothermal approaches, which were characterized structurally with single crystal X-ray diffraction (SCXRD), Fourier Transform infrared (FT-IR) spectroscopy, Thermogravimetric analysis (TGA) and elemental analysis (EA). For the treatment of the recurrent oral ulcers, their biological activity on recurrent oral ulcers was evaluated and the specific mechanism was also discussed. At first, this work detected the IL-18 (interleukin 18) and IL-1β (interleukin-1β) with enzyme linked immunosorbent assay (ELISA) detection. Besides, the activation for the signaling pathway of inflammatory was identified through real time reverse transcription-polymerase chain reaction (RT-PCR).

Two series of luminescent phosphonate coordination polymers of lanthanides for sensing ketones and Fe3+ in water

Two series of phosphonate coordination polymers (CPs) were designed and synthesized as probes for sensing certain pollutants in water. Six Ln phosphonate CPs, namely, Sm-HL1 (1), Pr-HL1(2), Nd-HL1(3), Sm-HL2(4), Pr-HL2(5), Nd-HL2(6) based on ((2′-cyano-[1,1′-biphenyl]-4-yl)methyl)phosphonic acid (HEtL1) 4′-((hydroxy(methoxy) phosphoryl)methyl)-[1,1′-biphenyl]-2-carboxylic acid (H2EtL2) were obtained by hydrothermal method. Their structures were confirmed and described through Single-crystal X-ray diffraction analysis, infrared spectra and thermogravimetric analysis. Their luminescence properties and sensing behaviors toward certain organic solvents and metal ions were detected and discussed. It was found that two types of CPs with different structures exhibited similar sensing ability toward iron ions and some ketone molecules, suggesting that the sensing activity might be mainly relative to the available uncoordinated oxygen atoms in the CPs rather than specific structures. The investigated CPs also showed good recyclability, guaranteeing its application as detecting probes.

Preparation of carbon dots-doped terbium phosphonate coordination polymers as ratiometric fluorescent probe for citrate detection

In this work, carbon dots-doped terbium phosphonate coordination polymers (CDs-GMP/Tb) were designed and prepared as ratiometric fluorescent probes for the detection of citrate. The as-prepared CDs-GMP/Tb are prepared and have the merits of high photostability, low toxicity, and excellent biocompatibility. The as-prepared CDs-GMP/Tb as ratiometric fluorescent probes also have better anti-interference ability and stability compared with the traditional single fluorescent probe. The surface morphology, fabrication, and spectroscopy were characterized through a variety of instruments. It confirms that the probes exhibited network structure doping carbon dots. With the addition of citrate, the fluorescence of GMP/Tb at 545 nm was significantly quenched, contrasting to the enhancement of fluorescence of CDs at 454 nm. Under optimum conditions, the detection limit for citrate was 0.47 μM, with a linear range of 0–200 μM between citrate concentrations and I545/I454. It has high sensitivity, selective, and rapid detection for citrate. The as-prepared CDs-GMP/Tb as ratiometric fluorescent probes were also used for imaging citrate in living cells. These experiment results showed that CDs-GMP/Tb as ratiometric fluorescent probes could be applied to trace citrate detection in the environmental and biological fields.

Controllable Macroscopic Chirality of Coordination Polymers through pH and Anion-Mediated Weak Interactions.

Helical architectures with controllable helical sense bias have recently attracted considerable interest for mimicking biological helices and developing novel chiral materials. Coordination polymers (CPs), composed of metal ion nodes and organic linkers, are intriguing systems showing tunable structures and functions. However, CPs with helical morphologies have rarely been explored so far. Particularly, chirality inversion through external stimulus has not been achieved in helical CPs. In this work, we carried out an in-depth investigation on the self-assembly of 1D gadolinium(III) phosphonate CPs using GdX3 (X=Cl, Br, I) and Gd(RSO3 ) (R=CH3 , C6 H5 , CF3 ) as metal sources and R-(1-phenylethylamino)methyl phosphonic acid (R-pempH2 ) as ligand. Superhelices were formed by precise control of the interchain interactions through different intercalated anions. Furthermore, the twisting direction of superhelices could be controlled by synergistic effect of anions and pH. This study may provide a new route to fabricate helical nanostructures of CPs with a desirable chiral sense and help understand the inner mechanism of the self-assembly process of macroscopic helical structures of molecular systems.

RETRACTED ARTICLE: Two transition metal phosphonate coordination polymers: application and nursing values on corneal disease during soft contact lenses usage

We, the Editors and Publisher of the journal Inorganic and Nano-Metal Chemistry, have retracted the following article: Su-Xiang Ma & Xiao-Ling Guo (2021): Two transition metal phosphonate coordination polymers: application and nursing values on corneal disease during soft contact lenses usage, Inorganic and Nano-Metal Chemistry, DOI: 10.1080/24701556.2021.1992428 Since publication, concerns have been raised about the integrity of the data in the article. When approached for an explanation, the authors have been unable to address the concerns raised and have not been able to provide sufficient supporting information. As verifying the validity of published work is core to the integrity of the scholarly record, we are therefore retracting the article. The corresponding author listed in this publication has been informed. The authors do not agree with the retraction. We have been informed in our decision-making by our policy on publishing ethics and integrity and the COPE guidelines on retractions. The retracted article will remain online to maintain the scholarly record, but it will be digitally watermarked on each page as ‘Retracted’.

Two three-dimensional mixed-ligated cobalt phosphonate coordination polymers: Syntheses, crystal structures and magnetic properties

Two new mixed-ligated cobalt phosphonates, Co5(pbtc)2(4,4′-bpy)2(H2O)4·2H2O (1) and Co4.5(pbtcH0.5)2(bpm)(H2O)6·4H2O (2) (pbtcH5 = 5-phosphonatophenyl-1,2,4-tricarboxylic acid, 4,4′-bpy = 4,4′-bipyridine and bpm = 2,2′-bipyrimidine), are obtained by incorporating 4,4′-bipyridine and 2,2′-bipyrimidine co-ligands, respectively. Compound 1 has infinite chains constructed by the alternative arrangement of Co3 trimers and Co2 dimers, which are connected by pbtc5− and 4,4′-bpy to form a three-dimensional framework structure. For compound 2, zigzag-like pentamers of Co are connected by pbtc5− and bpm ligands achieving a different type of three-dimensional framework structure. The lattice water molecules fill in the void space in the framework structures of both compounds. Magnetic measurements show that the antiferromagnetic interactions are dominated in compound 1, while the weak ferromagnetic exchange couplings are observed in compound 2.

Use of highly stable phosphonate coordination polymers as adsorbents for wastewater

A series of coordination polymers (CPs) based on phosphonates, M‐VP, and M‐Phen‐VP (M = Ce, La, Phen = 1,10‐phenanthroline, Im‐imidazole, VP = vinylphosphonate) were obtained by hydrothermal reactions in different conditions: room temperature, 75°C, 180°C, at pH 1.5–7 aqueous solutions. The materials were characterized by Fourier‐transform infrared (FTIR), X‐ray powder diffraction, and thermogravimetric analysis. The samples are characterized by a high degree of crystallinity, judging from the intensity of the peak in the 2θ region 8–9°. Thermogravimetric analysis performed on cerium and lanthanum CPs crystals indicate that the compounds are stable up to 360°C, after which it undergoes degradation corresponding to loss of the organic unit. The obtained materials were further used as adsorbent in the removal process of cesium (Cs(I)) and thalium ions (Tl(I)) from aqueous solutions. In order to establish the maximum adsorption capacity of the studied CPs and for the interpretation of the results obtained in the equilibrium study, several empirical isotherms were used: Freundlich, Temkin, Langmuir, and Dubinin–Radushkevich. The particular parameters for each isotherm and correlation coefficient (R2) have been determined.

Halogen bonding interactions assisted network expansion of a tetrahedral cobalt phosphonate coordination polymer bearing 4,4′-bipyridine ligand

A new cobalt phosphonate coordination polymer {[Co2(BrBzPO3)2(bpy)]∙2H2O}n (1) has been synthesized from the reactions of Co(NO3)2, 2-bromobenzyl phosphonic acid (BrBzP(O)(OH)2), and 4,4′-bipyridine (bpy) via reactants slow diffusion in H2O/ethanol solvent media at 60°C. Single-crystal X-ray diffraction analysis reveals that the Co(II) center has a {CoO3N} tetrahedral geometry. The coordinative network of 1 shows a layer structure constructed from Co–BrBzPO3 chains, which contain four-membered rings assembled from vertex-sharing {CoO3N} and {CPO3} tetrahedral units, connected by bpy linkers. It is worthy to note that net-to-net Br–Br halogen bonding interactions play the key supramolecular interactions to significantly dominate network expansion from a two-dimensional (3,4)-connected coordinative layer with a point symbol of (426)(42638) to a three-dimensional (4,4)-connected supramolecular network having a point symbol of (42638)(42638). Further, there are multiple noncovalent supramolecular interactions involving strong O–H∙∙∙O and weak C–H∙∙∙Br and C–H∙∙∙π interactions that provide powerful supports for stabilizing the whole crystal structure. Thermogravimetric (TG) analysis indicates that the coordinative network of 1 is high thermally stable upon heating to 340°C.

Polymeric layer framework and chain structure of two three-component cadmium and copper phosphonates embedded with pyrazine

Two metal phosphonate coordination polymers, [Cd2(H4tpmm)2(pz)2]n (1) and {[Cu2(H4tpmm)2(pz)2(H2O)4]·5H2O}n (2), have been synthesized from the self-assembly reactions of 2,4,6-tris(phosphorylmethyl)mesitylene (H6tpmm) with Cd(ClO4)2·6H2O or Cu(NO3)2·3H2O by introducing pyrazine (pz) as ancillary ligand. Cadmium phosphonate 1 possesses a layer framework, in which the two crystallographic distinct Cd(II) centers show two different coordination environments, one of which has a {CdO4N2} octahedral geometry in an approximately regular manner and the other suits a {CdO3N2} square pyramidal geometry. Copper phosphonate 2 displays a chain structure, in which the two crystallographic distinct Cu(II) centers both have the same {CuO4N2} octahedrons but distort in different ways; one is in a Jahn–Teller distortion while the other is in a rhombic distortion. For both Cd(II) and Cu(II) complexes, the pz ligand can be regarded to be embedded into the extended metal phosphonate architectures and form remarkable C–H … π interactions with the phenyl rings of the H4tpmm2− ligands, which cooperate with O–H⋯O hydrogen-bonding interactions in providing supports for stabilization. Thermogravimetric analysis reveals that 1 and 2 both are highly thermally stable with a decomposition process occurred at a temperature approaching 375 and 405 ​°C, respectively. The luminescence properties of 1 have also been studied.

SYNTHESES, Structures and Fluorescent Properties of Two Zn(II)-Diphosphonate Coordination Polymers

With the introduction of 2,2′-bipyridine (2,2′-bipy) agent, two new zinc coordination polymers (CPs), {[Zn6(HL-H)4(2,2′-bipy)4]·¼H2O}n1 and {[Zn3(HL-H)2(H2O)4]·6H2O}n2, have been hydrothermally obtained derived from diphosphonic acid, 1-hydroxy-2-(3-pyridyl)ethylidene-1,1-diphosphonic acid (H5L = (H4C5N)CH2C(OH)(PO3H2)2, HL-H = (H4C5N–H)CH2C(OH)(PO3)2), and determined by single-crystal X-ray diffractions, elemental analysis, IR, powder X-ray diffractions (PXRD). The single-crystal X-ray diffractions reveal that compound 1 owns a novel 1-D fishbone-like inorganic chain structure built from binuclear building blocks [Zn2(O–P–O)2]n via [ZnO4]n tetrahedron linkers. It is the first example that N-heterlcyclic amine 2,2′-bipy is used as the second ligand to construct the compound 1 with the diphosphonic acid ligand H5L. Both hydrogen bonding and π–π stacking interactions further extend the 1-D chain to the 3-D supramolecular network. Compound 2 exhibits a 2-D reticulate layer structure containing 4-, 8- and 16-membered rings created from 1-D ladder-like inorganic chain, and the organic pyridine rings in the structure point to voids defined by the 16-membered rings. Moreover, the room-temperature fluorescence measurements show that both the compounds display two fluorescent emissions centered at 379, 424 nm for 1 and 380, 424 nm for 2, respectively, caused by intraligand π*–π emission state of organic pyridine ring (λex = 235 nm). With the introduction of 2,2′-bipyridine (2,2′-bipy) agent, two new Zn(II)-phosphonate CPs, 1-D {[Zn6(HL-H)4(2,2′-bipy)4]·¼H2O}n1 and 2-D {[Zn3(HL-H)2(H2O)4]·6H2O}n2 (H5L = (H4C5N)CH2C(OH)(PO3H2)2, HL-H = (H4C5N–H)CH2C(OH)(PO3)2), have been hydrothermally obtained and characterized. The thermal stabilities and fluorescent properties of them have been investigated.

A phosphonate coordination polymer with highly sensitive detection of ascorbic acid and the proton conductivity of its polymer composites

A phosphonate coordination polymer, [Cd(H3bmpa)2]n (1), based on Cd2+ ions and H4bmpa (H4bmpa = N-Benzyliminobis(methylenephosphonicacid)) was synthesized under hydrothermal conditions. It is characterized by single crystal X-ray diffraction, PXRD and TGA. Crystal structure indicates that adjacent Cd2+ ions are linked by oxygen atoms in the phosphonate groups to form a 1D chain structure. Adjacent 1D chains are further linked by hydrogen bonds to form a 2D planar structure. Complex 1 is a bifunctional material that has both fluorescent and proton conducting properties. It can detect ascorbic acid sensitively and selectively with a detection limit of 5 µM. To further improve the proton conductivity of Complex 1, PVA (Polyvinyl alcohol) was introduced with it to prepare the composites. The proton conductivity of 1@PVA-10 is 3.05 × 10−5S·cm−1 (323 K, 98% RH), which is two orders of magnitude higher than that of coordination polymer.

Multiporous Terbium Phosphonate Coordination Polymer Microspheres as Fluorescent Probes for Trace Anthrax Biomarker Detection.

Lanthanide coordination polymers have been recently regarded as attractive sensing materials because of their selectivity, high sensitivity, and rapid response ability. In this research, the multiporous terbium phosphonate coordination polymer microspheres (TbP-CPs) were prepared as a novel fluorescent probe, which showed a fluorescence turn-on response capability for the detection of the trace anthrax biomarker dipicolinate acid (DPA). The morphology and chemical composition of as-prepared TbP-CPs were characterized in detail. The TbP-CPs have the vegetable-flower-like structure and microporous surface. In addition, the as-prepared TbP-CPs not only possess the merits of convenience and simple preparation with high yield but also have the excellent characters as fluorescent probes, such as high stability, good selectivity, and rapid detection ability within 30 s. This proposed sensor could detect DPA with a linear relationship in concentrations ranging from 0 to 8.0 μM and a high detection sensitivity of 5.0 nM. Furthermore, the successful applications of DPA detection in urine and bovine serum were demonstrated. As a result, the recovery ranged from 93.93-101.6%, and the relative standard deviations (RSD) were less than 5%.

PH-dependant synthesis, structures and luminescent properties of a series of novel lanthanide phosphonate coordination polymers

A series of two-dimensional layered lanthanide phosphonates, based on 4′-((hydroxy(methoxy)phosphoryl)methyl)-[1,1′-biphenyl]-2-carboxylic acid (H3L′ = HOOC-C6H4-C6H4-CH2-PO(OH)OCH3), Ln(HL)(H2L)(H2O) (H3L = HOOC-C6H4-C6H4-CH2-PO(OH)2), [Ln = La (1), Ce (2), Eu (3), Gd (4), Tb (5), La0.59Eu0.12Tb0.29 (6)] have been obtained by pH-dependent hydrothermal synthesis promoted by ultrasonic. Coordination polymers 1–6 are characterized by single-crystal X-ray diffraction analysis, elemental analysis, infrared spectroscopy, powder X-ray diffraction and thermogravimetry measurements. Their photoluminescence properties are investigated and found that the emission wavelength of 6 could be turned by varying the composition of Ln ions from ligand-centered blue light emission (La3+), to Ln-centered green (Tb3+) and red (Eu3+) light emission, exhibiting white light emission. The magnetic properties of 4 and 5 are also studied.

Communication—Iron(II)-Benzene Phosphonate Coordination Polymers as an Efficient Active Material for Negative Electrode of Lithium-Ion Batteries

An Iron based Metal-Organic Framework is proposed as an active material for negative electrode of lithium battery. The material is characterized by scanning electron microscope (SEM), powder X-ray diffraction (XRD), nitrogen uptake (BET) and thermogravimetric Analyses (TGA). Electrochemical properties have been determined by cyclic voltammetry and galvanostatic cycling in coin cells using lithium metal as counter electrodes. The electrochemical evaluation has revealed a significant enhancement in the capacity (550 mAh/g) with a mean voltage of 0.9 V vs Li+/Li compared to the actual graphite (300 mAh/g) or Li4Ti5O12 (170 mAh/g) and a good cyclability showing the interest of such material.

Temperature-controlled Cd(II)–phosphonate coordination polymers: Syntheses, crystal structures, and luminescent properties

Two temperature-controlled Cd(II)–phosphonate coordination polymers have been synthesized successfully. Compound {[Cd2(H4tpmb)(H2O)3]}n (1; H8tpmb=1,2,4,5-tetrakis(phosphorylmethyl)benzene) produced at 80°C adopts a three-dimensional network with a Cd:H2O ratio of 2:3, while compound {[Cd(H6tpmb)(H2O)4]·4H2O}n (2) synthesized at room temperature displays a zigzag one-dimensional chain structure with a Cd:H2O ratio of 1:4. The phosphonate ligand is partially deprotonation, being a form of H4tpmb4− in 1 and H6tpmb2− in 2, where the former shows a μ8-bridging mode with a cis,trans,cis,trans conformation while the latter adopts a μ2-bridging mode with a trans,cis,trans,cis conformation. These results indicate that water molecules make higher competition in coordinating with the Cd(II) center of such materials at room temperature, while at 80°C, the water molecules are more labile and the coordination of phosphonate to the Cd(II) center becomes dominant. This clearly illustrates a case of temperature-modulated complexation of phosphonate ligand and water molecule towards the Cd(II) center, which result in differences in ligand charges, ligand conformations, and coordination modes, leading to drastic variations of network topologies.

Hydrothermal synthesis of zinc(II)-phosphonate coordination polymers with different dimensionality (0D, 2D, 3D) and dimensionality change in the solid phase (0D→3D) induced by temperature

Three new zinc(II) coordination polymers, [Zn(HO3PCH2CH2COO)(C12H8N2)(H2O)] (1), [Zn3(O3PCH2CH2COO)2(C12H8N2)](H2O)3.40 (2) and [Zn5(HO3PCH2CH2COO)2(O3PCH2CH2COO)2(C12H8N2)4](H2O)0.32 (3), with different structural dimensionality (0D, 2D and 3D, respectively) have been prepared by hydrothermal synthesis, and their structures were determined by single-crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic system (P21/c) forming discrete dimeric units bonded through H-bonds, while compounds 2 and 3 crystallize in the triclinic (P−1) and the monoclinic (C2/c) systems, respectively. Compound 3, showing three different coordination numbers (4, 5 and 6) for the zinc atoms, has also been obtained by thermal treatment of 1 (probed by high-temperature XRPD experiments). The crystalline features of these compounds, related to the coordination environments for the zinc atoms in each structure, provoke the increase of the relative fluorescence for 2 and 3, compared to the free phenanthroline. Thermal analysis (TG and DSC) and XPS studies have been also carried out for all compounds.

Structural Systematics and Topological Analysis of Coordination Polymers with Divalent Metals and a Glycine-Derived Tripodal Phosphonocarboxylate

A novel family of four hybrid metal phosphonate coordination polymers is reported that are constructed from divalent metal ions (Ca, Sr, Ba, and Pb) and BPMGLY (bis-phosphonomethylglycine, a phosphonated derivative of glycine). These compounds (and their compositions) are Ca-BPMGLY (CaBPMGLY·H2O), Sr-BPMGLY (SrBPMGLY·H2O), Ba-BPMGLY (Ba3.5(BPMGLY)2·6H2O), and Pb-BPMGLY (PbBPMGLY·H2O). They were obtained by hydrothermal reactions in acidic aqueous solutions (pH range 2.3–5.7) and fully characterized by physicochemical methods and structural analysis. Ca-BPMGLY, Sr-BPMGLY, and Pb-BPMGLY have very similar 3D coordination polymer structures, and the latter two are isostructural. In contrast to the Ca, Sr, and Pb analogs, Ba-BPMGLY possesses a different 2D layered network. These four new compounds, together with our previously reported 2D coordination polymer Mg-BPMGLY (MgBPMGLY·2H2O, Demadis et al. Inorg. Chem. 2012, 51, 7889–7896), were topologically classified revealing (i) the uninodal 3-connected net with the hcb topology in Mg-BPMGLY, (ii) the uninodal 5-connected nets with the bnn and vbj topology in Ca-BPMGLY and Sr-BPMGLY, respectively, and (iii) the very complex topologically unique hexanodal 4,4,6,6,7,8-connected net in Ba-BPMGLY. The vbj topology was also identified in the related Pb-BPMGLY 3D framework. These topological features show that the complexity of BPMGLY-driven 2D and 3D metal–organic networks increases periodically following the Mg < Ca ≤ Sr ≪ Ba trend.

Structures and Spectroscopy Studies of Two M(II)-Phosphonate Coordination Polymers Based on Alkaline Earth Metals (M = Ba, Mg)

The two examples of alkaline-earth M(II)-phosphonate coordination polymers, [Ba2(L)(H2O)9]·3H2O (1) and [Mg1.5(H2O)9]·(L-H2)1.5·6H2O (2) (H4L = H2O3PCH2N(C4H8)NCH2PO3H2),N,N′-piperazinebis(methylenephosphonic acid), (L-H2= O3PH2CHN(C4H8)NHCH2PO3) have been hydrothermally synthesized and characterized by elemental analysis, FT-IR, PXRD, TG-DSC, and single-crystal X-ray diffraction. Compound1possesses a 2D inorganic-organic alternate arrangement layer structure built from 1D inorganic chains through the piperazine bridge, in which the ligand L−4shows two types of coordination modes reported rarely at the same time. In1, both crystallographic distinct Ba(1) and Ba(2) ions adopt 8-coordination two caps and 9-coordination three caps triangular prism geometry structures, respectively. Compound2possesses a zero-dimensional mononuclear structure with two crystallographic distinct Mg(II) ions. Free metal cations [MgO6]n2+and uncoordinated anions(L-H2)n2-are joined together by static electric force. Results of photoluminescent measurement indicate three main emission bands centered at 300 nm, 378.5 nm, and 433 nm for1and 302 nm, 378 nm, and 434.5 nm for2(λex=235 nm), respectively. The high energy emissions could be derived from the intraligandπ∗-ntransition stations ofH4L(310 nm and 382 nm,λex=235 nm), while the low energy emission (&gt;400 nm) of1-2may be due to the coordination effect with metal(II) ions.