Metal Phosphonate Chemistry

Clearfield, Abraham

doi:10.1002/9780470166482.ch4

Cited by 440 publications

(148 citation statements)

References 218 publications

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“…[21] Consequently, this rich structural variability may offer new possibilities for potential applications. Whereas swelling/shrinkage upon ammonia and amine adsorption/desorption is a well-known effect for layered compounds, [22] the high basicity of these guest species usually results in highly disordered solids and prevents further structural characterization of the intercalation compounds.…”

Section: Introductionmentioning

confidence: 99%

“Breathing” in Adsorbate‐Responsive Metal Tetraphosphonate Hybrid Materials

Colodrero

Cabeza

Olivera‐Pastor

et al. 2009

Chemistry A European J

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The structures of various layered calcium tetraphosphonates (CaH6DTMP; H8DTMP=hexamethylenediamine tetrakis(methylenephosphonic acid)), have been determined. Starting from CaH6DTMP.2H2O, thermal treatment and subsequent exposure to NH3 and/or H2O vapors led to four new compounds that showed high storage capacity of guest species between the layers (up to ten H2O/NH3 molecules) and a maximum volume increase of 55 %. The basic building block for these phosphonates consists of an eight-membered ring chelating Ca2+ through two phoshonate groups, and the organic ligand is located within the layers, which are held together by hydrogen bonds. The structural analysis revealed that the uptake/removal of guest species (H2O and NH3) induces significant changes in the framework not only by changing the interlayer distances but also through important conformational changes of the organic ligand. An anisotropic breathing motion could be quantified by the changes of the unit-cell dimensions and ligand arrangements in four crystalline derivatives. Complete characterization revealed the existence of interconversion reactions between the different phases upon gas uptake and release. The observed behavior represents, to the best of our knowledge, the first example of a breathing-like mechanism in metal phosphonates that possess a 2D topology.

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Section: Introductionmentioning

confidence: 99%

“Breathing” in Adsorbate‐Responsive Metal Tetraphosphonate Hybrid Materials

Colodrero

Cabeza

Olivera‐Pastor

et al. 2009

Chemistry A European J

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“…One of the potential remedies to this problem is the use of adsorption technologies. Activated carbons 3 and a number of low-cost adsorbents such as agricultural residues and peat [4][5][6][7] have been used for the removal of heavy metal cations. However, the major disadvantages of these adsorbents are their low loading capacities and their relatively weak interactions with metallic cations, as evidenced by low metal ion binding constants 8,9 .…”

Section: Introductionmentioning

confidence: 99%

Study on the adsorption of heavy metal ions from aqueous solution on modified SBA-15

Giraldo

Moreno–Piraján

2013

Mat. Res.

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Amino-functionalized SBA-15 mesoporous silica was prepared, characterized, and used as an adsorbent for heavy metal ions. The organic-inorganic hybrid material was obtained by a grafting procedure using SBA-15 silica with 3-aminopropyl-triethoxysilane and bis(2,4,4-trimethylpentyl) phosphinic acid (Cyanex 272), respectively. The structure and physicochemical properties of the materials were characterized by means of elemental analysis, X-ray diffraction (XRD), nitrogen adsorption-desorption, thermogravimetric analysis, FTIR spectroscopy and immersion calorimetry. The organic functional groups were successfully grafted onto the SBA-15 surface and the ordering of the support was not affected by the chemical modification. The behavior of the grafted solids was investigated for the adsorption of heavy metal ions from aqueous solutions. The hybrid materials showed high adsorption capacity and high selectivity for zinc ions. Other ions, such as cooper and cobalt were absorbed by the modified SBA-15 material.

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“…The understanding of the role of the chloroform molecule in the solid phase is important for the structure and stability of the crystal. As a first step we reported the LT crystal structure of the title associate [1]. RT structure and spectroscopic results will be compared and analyzed in light of a possible disorder model.…”

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confidence: 99%

“…Bisphosphonic acids have attracted close attention because of their utility in supramolecular chemistry and crystal engineering [1,2]. Usually, the metal bisphosphonates form polymeric materials and microporous solids, with properties that offer a diversity of practical applications in catalysis, ion-exchange and sorption [2][3][4].…”

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confidence: 99%

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Molecular association in the dichloridobis(2-methoxydibenzo[c,e]-[1,2]oxaphosphorine-κP)platinum(II):trichloromethane 1:1 solvate

Holczbauer¹,

Németh²,

Pfeifer³

et al. 2009

Acta Cryst Sect A

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The X-ray structure determination of the oxaphosphorineplatinum-dichloride complex showed that it crystallized with one chloroform solvent molecule. The solvent molecules are stuck in channels made up by the complex molecules. These open solvent tubes are parallel to the crystallographic a axis and penetrate the macroscopic crystals throughout. Each chloroform molecule connects to its complex molecule via a pronounced C-H ... O bond. The chloroform molecules are clearly disordered. To decide the dynamic or static nature of disorder X-ray diffraction data were collected at low and at room temperatures, too. IR and Raman spectroscopy were also used to determine the binding angles and the intermolecular C-H ... O bonds' characteristics. The understanding of the role of the chloroform molecule in the solid phase is important for the structure and stability of the crystal. As a first step we reported the LT crystal structure of the title associate [1]. RT structure and spectroscopic results will be compared and analyzed in light of a possible disorder model. [1,2]. Usually, the metal bisphosphonates form polymeric materials and microporous solids, with properties that offer a diversity of practical applications in catalysis, ion-exchange and sorption [2][3][4]. Hydrogen bonds are predominant in these architectures, producing one-, two-and three-dimensional networks. In our continuing research for bisphosphonate ester derivatives, we have prepared three new Cd complexes of (dichloromethylene) bisphosphonic acid P,P-diphenyl, monophenyl and monoethyl ester derivatives. The structures of these compounds were characterized by single crystal X-ray diffraction. All three compounds show a different layered structure. The Cd complex of monophenyl ester derivative consists of 1-D chains with four independent octahedral Cd atoms joined by two bisphosphonate ligands. The chains are connected into layers by phosphonate O atoms, and the adjacent layers are held together by weak π−π stacking interactions. The Cd complex of diphenyl ester derivatives shows a new type of layered structure for metal bisphosphonates, where the bisphosphonate ligand coordinates tridentately to three Cd 2+ ions. Each CdO 6 octahedron is connected to three CPO 3 tetrahedra and each tetrahedron to three octahedra leading to a 2-D framework consisting of 12-membered cyclic cores. In Cd compound of monoethyl ester derivative, the asymmetric unit contains two independent Cd 2+ cations connected by bisphosphonate ligands, to form a Cd−bisphosphonate layer. The layers are further interconnected into a 3-D supramolecular network by extensive hydrogen bonds. One of the oldest complex anion salts, used for long in the analytical chemistry of mainly foodstuffs and of inorganic chemistry is the Reinecke salt, conceived in the 1860s. Apart from early attempts no systematic structural studies were reported for this long-known substance, however. Crystallization of such compounds poses formidable problems as the title salt generally forms rather awkward precipitates...

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Metal Phosphonate Chemistry

Cited by 440 publications

References 218 publications

“Breathing” in Adsorbate‐Responsive Metal Tetraphosphonate Hybrid Materials

“Breathing” in Adsorbate‐Responsive Metal Tetraphosphonate Hybrid Materials

Study on the adsorption of heavy metal ions from aqueous solution on modified SBA-15

Molecular association in the dichloridobis(2-methoxydibenzo[c,e]-[1,2]oxaphosphorine-κP)platinum(II):trichloromethane 1:1 solvate

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