Metal Phosphonate Chemistry: From Synthesis to Applications - Rilegato

Rilegato

ISBN 10: 1849733562 ISBN 13: 9781849733564

Casa editrice: Royal Society of Chemistry, 2011

Riassunto

Metal phosphonate chemistry is a highly interdisciplinary field, as it encompasses several other areas, such as materials chemistry, gas storage, pharmaceutics, corrosion control, classical chemical synthesis, X-Ray crystallography, powder diffraction, etc. It has also acquired additional significance due to "Metal-Organic Frameworks", as evidenced by the hundreds of papers published each year. Currently there is no other book on the topic and this book fills the gap in the literature by summarising in a concise way the latest developments in the field. Metal phosphonate chemistry has seen impressive growth in the last 15-20 years and there is a clear need to systematize and organize all this growth. This unique book accomplishes just that need - edited by two experts, it includes contributions from other experienced researchers and organises, cateqorises and presents in an attractive way the latest hot topics in metal phosphonate chemistry and related applications. With an extensive bibliography, it is a great reference for academic and industrial researchers as well as students working in the field and will act as a starting point for further exploration of the literature. It is also of great interest to scientists working in the broader area of metal-organic frameworks and their applications.

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Informazioni sugli autori

Abraham Clearfield's research interests are focused on solid state and materials chemistry and encompass a wide variety of projects. An important goal is the ability to design and synthesize new materials whose structure and properties can be predicted and controlled. Layered compounds are amenable to manipulation to produce new structures because of the weak forces between layers and his group have learned how to separate the layers of several classes of compounds and are reconstituting them into novel materials. For example, photochemically active species may be encapsulated to produce permanently porous structures of controlled pore size - such compounds may prove to be selective catalysts. Layered proton conductors and self-assembled supramolecules of novel structures and properties have been prepared and some of these find utility in the separation of radioactive ions from nuclear waste. Zeolites are among the most powerful and versatile catalysts known and Professor Clearfield's group have initiated a program to synthesize new materials with pores in the 10-20+ range. These materials include organic-inorganic hybrids as well as mixed metal oxides. The research interests of Konstantinos D Demadis and his group include synthesis and structural characterization of metal phosphonate frameworks, and crystal engineering with an emphasis on hybrid materials synthesis. Applications that result from these efforts include gas sorption and storage, corrosion control, and interface chemistry. Other research interests include colloidal silica and silicates-containing composite materials, mechanistic studies on formation and dissolution of colloidal silica, and effects of polymers on colloidal silica properties. Silicon chemistry is pursued based on bioinspired and biomimetic approaches. An important part of Professor Demadis' research efforts includes synthesis, characterization, selection and utilization of dispersant homo-, co-, and terpolymers, study of polymer/surface interactions, precipitation, inhibition and dissolution kinetics of sparingly soluble salts. The research projects are augmented by a multitude of analytical and instrumental techniques, such as solution and solid state NMR, far, near and mid FT-IR, electronic spectroscopy (UV-visible), Scanning Electron Microscopy (SEM), X-Ray Fluorescence, and X-ray chemical crystallography. Thus far, his group thus has published more than 100 peer-reviewed papers, 11 book chapters, 2 books and 2 patents.

Abraham Clearfield's research interests are focused on solid state and materials chemistry and encompass a wide variety of projects. An important goal is the ability to design and synthesize new materials whose structure and properties can be predicted and controlled. Layered compounds are amenable to manipulation to produce new structures because of the weak forces between layers and his group have learned how to separate the layers of several classes of compounds and are reconstituting them into novel materials. For example, photochemically active species may be encapsulated to produce permanently porous structures of controlled pore size - such compounds may prove to be selective catalysts. Layered proton conductors and self-assembled supramolecules of novel structures and properties have been prepared and some of these find utility in the separation of radioactive ions from nuclear waste. Zeolites are among the most powerful and versatile catalysts known and Professor Clearfield's group have initiated a program to synthesize new materials with pores in the 10-20+ range. These materials include organic-inorganic hybrids as well as mixed metal oxides. The research interests of Konstantinos D Demadis and his group include synthesis and structural characterization of metal phosphonate frameworks, and crystal engineering with an emphasis on hybrid materials synthesis. Applications that result from these efforts include gas sorption and storage, corrosion control, and interface chemistry. Other research interests include colloidal silica and silicates-containing composite materials, mechanistic studies on formation and dissolution of colloidal silica, and effects of polymers on colloidal silica properties. Silicon chemistry is pursued based on bioinspired and biomimetic approaches. An important part of Professor Demadis' research efforts includes synthesis, characterization, selection and utilization of dispersant homo-, co-, and terpolymers, study of polymer/surface interactions, precipitation, inhibition and dissolution kinetics of sparingly soluble salts. The research projects are augmented by a multitude of analytical and instrumental techniques, such as solution and solid state NMR, far, near and mid FT-IR, electronic spectroscopy (UV-visible), Scanning Electron Microscopy (SEM), X-Ray Fluorescence, and X-ray chemical crystallography. Thus far, his group thus has published more than 100 peer-reviewed papers, 11 book chapters, 2 books and 2 patents.

Dalla quarta di copertina

Metal phosphonate chemistry is a highly interdisciplinary field, as it encompasses several other areas, such as materials chemistry, gas storage, pharmaceutics, corrosion control, classical chemical synthesis, X-ray crystallography, powder diffraction, etc. It has also acquired additional significance due to "Metal-Organic Frameworks", as evidenced by the hundreds of papers published each year. This book fills the gap in the literature by summarising, in a concise way, the latest developments in the field. Metal phosphonate chemistry has seen impressive growth in the last 15-20 years and there is a clear need to systematize and organize all this growth. This unique book accomplishes just that need - edited by two experts, it includes contributions from other experienced researchers and organises, categorises and presents in an attractive way the latest hot topics in metal phosphonate chemistry and related applications. With an extensive bibliography, it is a great reference for academic and industrial researchers as well as students working in the field and will act as a starting point for further exploration of the literature. It is also of great interest to scientists working in the broader area of metal-organic frameworks and their applications.

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Metal Phosphonate Chemistry

From Synthesis to Applications

By Abraham Clearfield, Konstantinos Demadis

The Royal Society of Chemistry

Copyright © 2012 Royal Society of Chemistry
All rights reserved.

ISBN: 978-1-84973-356-4

Contents

Chapter 1 The Early History and Growth of Metal Phosphonate Chemistry Abraham Clearfield, 1, 
Chapter 2 Zirconium Phosphonates Riccardo Vivani, Ferdinando Costantino and Marco Taddei, 45, 
Chapter 3 High-throughput Methods for the Systematic Investigation of Metal Phosphonate Synthesis Fields Palanikumar Maniam and Norbert Stock, 87, 
Chapter 4 Metal Carboxyphosphonates Aurelio Cabeza and Miguel A. G. Aranda, 107, 
Chapter 5 Metal Phosphonates and Arsonates Containing an Auxiliary Ligand Jiang-Gao Mao, 133, 
Chapter 6 Synthesis of Phosphonic Acids and Their Esters as Possible Substrates for Reticular Chemistry Jerzy Zon Piotr Garczarek and Michal Bialek, 170, 
Chapter 7 Structural Chemistry of Bimetallic Oxides Constructed from Molybdodiphosphonate Building Blocks Stephanie Jones and Jon Zubieta, 192, 
Chapter 8 Structural and Magnetic Studies of Cobalt Phosphonates Li-Min Zheng and Yan Duan, 235, 
Chapter 9 How Laminar Zirconium Phosphates Can Make Organic Molecules Display New Behavior and Properties at the Supramolecular Level in the Solid State Ernesto Brunet, 279, 
Chapter 10 Open Framework and Microporous Metal Phosphonate MOFs with Piperazine-based Bisphosphonate Linkers Michael T. Wharmby and Paul A. Wright, 317, 
Chapter 11 Secondary Building Units and Framework Structures in Aluminium and Zinc Phosphates: The Connection Between R. Murugavel and C. N. R. Rao, 344, 
Chapter 12 Structural Studies of Paramagnetic Molecular Phosphonates Kandasamy Gopal, Shoaib Ali and Richard E. P. Winpenny, 364, 
Chapter 13 Application of Metal Phosphonates to Biotechnologies Bruno Bujoli, Pascal Janvier and Marc Petit, 420, 
Chapter 14 Structural Diversity in Metal Phosphonate Frameworks: Impact on Applications Konstantinos D. Demadis and Nikoleta Stavgianoudaki, 438, 
Chapter 15 Metal Organophosphonate Proton Conductors George K. H. Shimizu, Jared M. Taylor and Karl W. Dawson, 493, 
Chapter 16 Luminescent Metal Phosphonate Materials Gary B. Hix, 525, 
Chapter 17 N-(Phosphonomethyl)iminodiacetic Acid in the Construction of Coordination Polymers Filipe A. Almeida Paz and João Rocha, 551, 
Chapter 18 Uranyl Phosphonates: A Structural Survey Karah E. Knope and Christopher L. Cahill, 586, 
Chapter 19 Structural Chemistry of Transuranium Phosphonates Juan Diwu and Thomas Albrecht-Schmitt, 607, 
Subject Index, 632, 

CHAPTER 1

The Early History and Growth of Metal Phosphonate Chemistry

ABRAHAM CLEARFIELD

Department of Chemistry, Texas A&M University, College Station, USA 77843-3255

1.1 Early History of α-Zirconium Phosphonates

It is fitting that we begin with a history of the formation and growth of metal phosphonate chemistry. In 1978 Giulio Alberti et al. prepared a number of zirconium phosphonates by the direct reaction of phosphonic acids with ZrIV. In general

ZrIV + 2RPO3H2 -> Zr(O3PR)2 + 2H+ (1.1)

where R is an alkyl or aryl group. It was recognized that these compounds were layered in nature but no structures were forthcoming because of their very sparingly soluble nature. It was not until 1993 that the structure of the phenylphosphonate Zr(O3PC6H5)2 was solved by Poojary et al., based on a sample prepared in Alberti's laboratory. This synthesis required hydrothermal treatment for 30 days at 190–200 1C in the presence of HF as a solubilizing agent. The crystalline powder yielded unit cell dimensions a = 9.0985(5) Å, b = 5.4154(3) Å, c = 30.235(2) Å, β = 101.333(5)°, space group C2/c. The structure (Figure 1.1) is indeed layered and similar to that of α-zirconium phosphate, Zr(O3POH)2 · H2O. The unit cell dimensions of the phosphate (abbreviated α-ZrP), in space group P21/n: are a = 9.060(2) Å, b = 5.297(1) Å, c = 15.414(3) Å, β = 101.71(2)°. The a and b dimensions are very close to the corresponding dimensions of the phenylphosphonate but in this latter structure the phenyl rings are tilted 30° relative to the layers (Figure 1.1) whereas the P–OH groups of α-ZrP are almost perpendicular to the layers. This difference arises from the space group requirements. In P21/n the Zr4+ ion is slightly above and below the mean layer plane but in C2/c the metal ion lies exactly in the plane. The interlayer distances are 7.55 Å and 14.87 Å for the phosphate and phosphonate, respectively.

Subsequent to Alberti's discovery, a large number of similar compounds with many different functional groups were prepared, some of which are listed in Table 1.1. All of them have the α-ZrP structure. (See Chapter 2 for additional details.)

It is possible to prepare layered compounds of group 4 metals with two ligands such as phenyl and methyl groups. The ability to prepare such compounds with two pendant groups has some appealing features. If one group is large, as for example a biphenyl or long chain alkyl group and the other small, then micro-porosity is built into the structure. However, there are some pitfalls. If the small group is present in excess of 50%, interdigitation may occur removing part or all of the porosity. Further the composition obtained may be different than the starting composition and this may depend upon the synthesis conditions, particularly temperature and choice of solvent and whether HF is present. Another factor depends upon the relative hydrophobic–hydrophilic nature of the two ligands. In such cases the complete mixing may not be possible. However, it may be possible to achieve porosity and functionality, even between hydrophobic and hydrophilic species by choice of the ligands. As an example, mixed derivatives such as Zr(O3PC6H5)2–x (O3PCH2COOH)x introduces ion exchange capability and possible further reactivity at the carbonyl site.

1.1.1 Advent of γ-Zirconium Phosphonates

γ-Zirconium phosphonates are obtained by ester interchange of a phosphonic acid with γ-ZrP. Thus, it is necessary to understand the structure of γ-ZrP before continuing further. This compound was first prepared by refluxing a solution of ZrOCl2 in phosphoric acid containing a high concentration of ammonium or sodium phosphates. This procedure yields the half ammonium exchanged or sodium exchanged salt. Treatment with dilute HCl provides the protonated α-ZrP. The composition is Zr(PO4) [O2P(OH)2] · 2H2O. The structure was first solved incompletely from X-ray powder data on the titanium phase and later completely for Zr. The crystals are monoclinic, a = 5.3825(2) Å, b = 6.6337(1) Å, c = 12.4102(4) Å, β = 98.687(2)°, space group P21. The layers consist of phosphate groups within the layer bonding through oxygen atoms to four different Zr ions. Four such phosphate tetrahedra bond to a single Zr ion as shown in Figure 1.2. The coordination number of each Zr is six, the remaining two bonds are supplied by the dihydrogen phosphate groups. These groups bridge across two Zr ions in the a axis direction, tying together the chains running along the b axis direction into layers. The two hydroxyl groups are pendant, pointing into the interlayer space. They hydrogen bond to the water molecules, as shown in Figure 1.2, bringing the layers together. The γ-ZrP has been found to undergo ester interchange reactions by a topotactic mechanism. The group replaced is O2P(OH)2 and if phenyl phosphonic acid is interchanged, the in-going group is C6H5PO32- (as shown in Figure 1.3). Alberti points out that if the in-going groups are too bulky or of the type O2P(C6H5)2, steric hindrance may occur and only a portion of the sites can be occupied. While the Alberti group has dominated the use of topotactic exchange reactions with γ-ZrP, the first reactions were carried out by Yamanaka and his co-workers.

1.1.1.1 Early Chemistry of Zirconium Diphosphonates

Martin Dines and his co-workers prepared many zirconium phosphonates, much of which is in the patent literature. The idea behind their study was to prepare catalysts, so many of the phosphonates contained functional groups such as sulfonic acid, carboxylic acid, and other functionalities. However, an important advance was made by the Dines group when they introduced α,ω-diphosphonic acids. These compounds were layered but with interlayer spacings as shown in Table 1.1. These interlayer spacings indicate that the ligands were situated almost perpendicular to the layers and cross-linked them. The distance between these ligands, acting as pillars as in Figure 1.4, is 5.3 Å, leaving no porosity between pillars. Porosity was obtained by spacing the pillars by including phosphorous acid as a reactant. However, their data showed that a maximum in surface area was obtained when the mole percent pillar was 50% with a surface area of 390 m2 g-1. What they did not explain is that the compound with 100% pillars had a surface area of 316 m2 g-1. In point of fact, the parent compound Zr(O3PC6H4-C6H4 PO3) is porous. Direct determination of the structure of the compound is not possible because the X-ray powder pattern consists of only a few very broad peaks. Thus, the mystery is why the fully pillared compound has such a large surface area. More about this subject will be presented in Section 1.7.

1.2 Divalent Metal Phosphonates

Ten years after Alberti's publication on the zirconium monoaryl and alkyl derivatives, Mallouk et al. presented crystal structures of Mn, Zn, Co and Mg phenyl, and alkyl phosphonates. They all have the same layered structure with unit cell dimensions for the zinc compound a = 5.634(2) Å, b = 14.339(5) Å, c = 4.833(2) Å with Z = 2 and space group Pmn21. The composition of these compounds is M(O3PR) · H2O where R is the aryl or alkyl group. The metals are six coordinate but there are only three phosphonate oxygens versus six for the four valent layered compounds. The required coordination is obtained by a sharing of oxygen atoms as shown in Figure 1.5. Two of the phosphonate oxygen atoms chelate the metal ion and then both of these oxygen atoms donate to adjacent metal atoms. These oxygens are three coordinate and they are situated above and below the mean plane of the layer. A fifth coordination site is filled by the third phosphonate oxygen atom that connects these rows of metal atoms aligned along the a axis direction to create the layer. The sixth site is occupied by the water molecule. In the study of the zinc phenylphosphonate structure the phenyl rings were shown to be disordered. Closer inspection of the data revealed weak reflections requiring a doubling of the c axis. Refinement in this larger cell showed the phenyl rings in adjacent small cells to be rotated 90° from each other. Removal of the water molecule creates an open coordination site which can be occupied by primary amines. In a similar study only NH3 was taken in from the gas phase by the zinc phosphonate. After dehydration of the zinc hydrate at 200 °C under vacuum, liquid primary amines were readily intercalated. In the case of the mixed derivatives phosphite phosphonates, Zn(O3PH)x (O3PC6H5)1–x a certain amount of branched chain amines were also taken up. Crystal structures of the amine intercalates revealed the mechanism of the intercalation reaction. In the hydrated state the layers have a crenellated or zigzag appearance but in the intercalate the zinc atoms are four coordinate of distorted tetrahedral geometry. The metal bonds to three oxygens from three separate phosphonate groups and an amine nitrogen. In the process the crenellated shape straightens into a rather flat layer. This process is reversible.

Copper phosphonate structures are an exception to the six-coordinate first row transition metal phosphonates as the copper atoms are five coordinate for the phenyl and methyl compounds. Although the composition is the same, Cu(O3PR) · H2O, the copper coordination is distorted tetragonal pyramidal. The structure of Cu(O3PCH3) is layered, one oxygen atom from each phosphonate bonds to two copper ions forming a chain while the remaining two phosphonate oxygen atoms bond to two copper ions in an adjacent chain forming the layers. The base of the pyramid consists of three phosphonate oxygen atoms and the coordinated water molecule. The apical oxygen comes from an adjacent phosphonate oxygen atom and this bond distance is more than 0.3 Å longer than the Cu–O equatorial bonds. The copper phenylphosphonate has a similar layered structure but the phenyl rings within the interlamellar region are tilted to each other at a 98° angle.

Two copper arylenes were prepared in which the 1,4-phenylenebis(phosphonic acid) yielded a layered compound of composition Cu2(O3 PC6H4-PO3)(H2O)2 whereas the compound prepared with 4,4'-biphenylenebis-(phosphonic acid) retained two protons, Cu(HO3PC12H8PO3H). In both cases the copper coordination is square planar. Subsequently we synthesized a series of copper α,ω-alkylenebis (phosphonates) with 2 and 3 carbon chains and with 4 and 5 carbon chains; all four structures were solved utilizing X-ray powder data. The general formula for all the compounds is Cu2 [(O3 PCnH2nPO3) (H2O)2]. The copper coordination is distorted square pyramidal with bonding by four phosphonate oxygen atoms and one water molecule. The metal–oxygen bridging interactions form layers that are then connected to each other by the alkylene groups to form 3D structures. The three carbon chains form open rings with the layers and the water molecules protrude into the pores. These pores fill with water that hydrogen bonds to the bonded water molecules. The layer alkylene chain compounds are six coordinate, CuO4(OH2)2, forming layers that are cross-linked by the alkyl chains. This pillared arrangement creates tunnels running parallel to the c axis direction and contain additional water molecules. These water molecules are readily replaced by ammonia molecules.

Zinc compounds with two and three carbon chains were also prepared. In Zn2[(O3PC2H4PO3) (H2O)] the phosphonate groups chelate the Zn ions and bridge to neighboring zinc ions. The third phosphonate oxygen links these rows to form a layer and a water molecule bonds to zinc forming distorted octahedra. This type of bonding is similar to that in Figure 1.5 but in this case the layers are tied together by the ethylene groups. However, the unit cell extends over two layers as the ethyl groups point in opposite directions in adjacent layers. The C3 compound is anhydrous, Zn2(O3 PC3H6PO3). The zinc ions are tetrahedrally coordinated and corner shared with the phosphonate group leaving empty spaces within the layer. The unit cell extends over two layers (c = 18.865(1) Å).

Two additional zinc compounds were synthesized using 1,3-propylenbis-(phosphonic acid). In Zn(HO3PC3H6PO3H) the Zn ions are tetrahedrally coordinated by four oxygen atoms, two each from two independent phosphonate groups. The remaining third oxygen atom of both groups is protonated. The metal phosphonate interactions lead to double chains that are held together through the organic linkages leading to 2D sheets. These in turn are connected though hydrogen bonding forming a 3D metal phosphonate net- work. In the second compound, Zn3[(HO3PC3H6 PO3)2] · 2H2O, there are two independent zinc ions, one in a general position and one in a special position providing six zinc ions per unit cell. They are both four coordinate but Zn1 is coordinated by four phosphonate oxygen atoms and Zn2 by two water molecules and two phosphonate oxygen atoms. The structure contains large pores; however, no surface areas were obtained for this compound or the Zn2(O3PC3 H6PO3) compound.

The main group elements such as calcium and magnesium are known to yield multiple phases other than those of the transition elements. Larger cations such as Pb2+ form eight coordinate structures and in acid solution may form 1:2 derivatives such as M(HO3PC6 H5)2. In these compounds both phosphonate groups chelate the metal ions and one oxygen of each chelate coordinates to an adjacent metal ion. The remaining oxygen atoms cross-link these chains into layers.

1.3 Trivalent Metal Phosphonates

At this juncture a word about solubility is in order. We have seen that the four-valent aryl and many alkyl phosphonates are noncrystalline. This feature may be attributed to the great insolubility of these compounds. The few crystalline compounds usually contain fluoride ions and are prepared in strong HF solutions. However, inclusion of nitrogen or other hydrophilic groups into the phosphonic acid changes the solubility of the MIV complex to the point that crystallization may occur. Three-valent phosphonates are more soluble, leading to many crystalline compounds. Almost all divalent phosphonates are soluble in slightly acidic media and can be crystallized by slow evaporation of solutions or by addition of a second solvent or layering. All monovalent phosphonates are highly soluble and readily crystallizable. We shall illustrate that in Section 1.11.

(Continues...)

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Dettagli dell'edizione

• Editore: Royal Society of Chemistry
• Data di pubblicazione: 2011
• Lingua: Inglese
• ISBN 10: 1849733562
• ISBN 13: 9781849733564
• Rilegatura: Copertina rigida
• Numero di pagine: 655
• Redattore: Clearfield Abraham, Demadis Konstantinos
• Contatto del produttore: non disponibile
• Persona responsabile: non disponibile