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Functional Metal Phosphonates

Functional Metal Phosphonates PDF Author: Houston Phillipp Perry
Publisher:
ISBN:
Category :
Languages : en
Pages :

Book Description
The primary goal of the work described in this dissertation was the incorporation of functionality into metal phosphonates. This was done in one of several ways. The first involved using phosphonate ligands that had covalently attached organic functional groups. In some cases, these ligands undergo reactions during the solvothermal syntheses which can impart new chemical reactivity. Another method used to introduce functionality was to partially or completely substitute metal atoms within phosphonate clusters to create materials which may have interesting magnetic properties. By controlling the way these clusters pack in the solids, their magnetic properties may be able to be augmented. The final method used to impart functionality to metal phosphonates was the incorporation of N-donor and bulky aryl groups into the phosphonate ligands. These influences caused structural variations which exposed potentially active sites within the materials, including both Lewis acidic and basic sites, as well as Bronsted acid sites. The first strategy was employed in the design of tetravalent metal phosphonates which have covalently incorporated bipyridine moieties. The materials are porous so that the bipyridine sites can chelate Pd atoms from solution, which can then be reduced to stable nanoparticles trapped within the phosphonate matrix. This approach was also used in the synthesis of surface-functionalized divalent metal phosphonates which exhibit interesting amine uptake properties. Solvent and cation substitution effects were used to control the packing and connectivity of phosphonate-based clusters. The selective substitution of metal atoms within the clusters may lead to interesting magnetic materials. In other work, N-donor and bulky phosphonates were used to influence the structure of several SnII phosphonates, which resulted in the discovery of a new layered structure type. The effect of the Sn-N interaction on the structures is investigated, and found to have significant effects on the structural units formed and how they pack in the solid state. The work presented herein represents only a small fraction of the rich chemistry of metal phosphonates. Creative researchers will continue to push boundaries and find new and interesting applications for phosphonate-based materials.

Functional Metal Phosphonates

Functional Metal Phosphonates PDF Author: Houston Phillipp Perry
Publisher:
ISBN:
Category :
Languages : en
Pages :

Book Description
The primary goal of the work described in this dissertation was the incorporation of functionality into metal phosphonates. This was done in one of several ways. The first involved using phosphonate ligands that had covalently attached organic functional groups. In some cases, these ligands undergo reactions during the solvothermal syntheses which can impart new chemical reactivity. Another method used to introduce functionality was to partially or completely substitute metal atoms within phosphonate clusters to create materials which may have interesting magnetic properties. By controlling the way these clusters pack in the solids, their magnetic properties may be able to be augmented. The final method used to impart functionality to metal phosphonates was the incorporation of N-donor and bulky aryl groups into the phosphonate ligands. These influences caused structural variations which exposed potentially active sites within the materials, including both Lewis acidic and basic sites, as well as Bronsted acid sites. The first strategy was employed in the design of tetravalent metal phosphonates which have covalently incorporated bipyridine moieties. The materials are porous so that the bipyridine sites can chelate Pd atoms from solution, which can then be reduced to stable nanoparticles trapped within the phosphonate matrix. This approach was also used in the synthesis of surface-functionalized divalent metal phosphonates which exhibit interesting amine uptake properties. Solvent and cation substitution effects were used to control the packing and connectivity of phosphonate-based clusters. The selective substitution of metal atoms within the clusters may lead to interesting magnetic materials. In other work, N-donor and bulky phosphonates were used to influence the structure of several SnII phosphonates, which resulted in the discovery of a new layered structure type. The effect of the Sn-N interaction on the structures is investigated, and found to have significant effects on the structural units formed and how they pack in the solid state. The work presented herein represents only a small fraction of the rich chemistry of metal phosphonates. Creative researchers will continue to push boundaries and find new and interesting applications for phosphonate-based materials.

Metal Phosphonate Chemistry

Metal Phosphonate Chemistry PDF Author: Abraham Clearfield
Publisher: Royal Society of Chemistry
ISBN: 1849733562
Category : Science
Languages : en
Pages : 676

Book Description
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.

Metal Phosphonates and Phosphinates

Metal Phosphonates and Phosphinates PDF Author: Marco Taddei
Publisher: MDPI
ISBN: 3039280023
Category : Mathematics
Languages : en
Pages : 120

Book Description
The present Special Issue of Symmetry is devoted to two important areas of global Riemannian geometry, namely submanifold theory and the geometry of Lie groups and homogeneous spaces. Submanifold theory originated from the classical geometry of curves and surfaces. Homogeneous spaces are manifolds that admit a transitive Lie group action, historically related to F. Klein's Erlangen Program and S. Lie's idea to use continuous symmetries in studying differential equations. In this Special Issue, we provide a collection of papers that not only reflect some of the latest advancements in both areas, but also highlight relations between them and the use of common techniques. Applications to other areas of mathematics are also considered.

Functional Metal-Organic Frameworks

Functional Metal-Organic Frameworks PDF Author: Ali Morsali
Publisher: John Wiley & Sons
ISBN: 1119640431
Category : Science
Languages : en
Pages : 256

Book Description
Owing to the extensive interest in construction of functional metal organic frameworks (FMOFs), this book discusses the roles of functional groups on the structure and application of metal organic frameworks (MOFs). The contents of the book are classified based on the structural and chemical properties of organic functions, in order to make readers able to compare the different effects of each function on the structure and application of the MOFs. In each chapter, the chemical properties of applied functional groups are gathered to give deeper insight into the roles of organic functions in the structure and application of MOFs. In the function-application properties, the authors discuss how a functional group can dominate the host-guest chemistry of the MOFs and how this host-guest chemistry can expand the effectiveness and efficiency of the material in different fields of applications. Finally, function-structure properties are discussed. In function-application properties, it is discussed how a functional group can affect the topology, porosity, flexibility and stability of the framework. The features of this subject are novel and are presented for the first time.

Synthesis and Characterization of Porous Metal Phosphonates

Synthesis and Characterization of Porous Metal Phosphonates PDF Author: Tiffany L. Kinnibrugh
Publisher:
ISBN:
Category :
Languages : en
Pages :

Book Description
This dissertation focuses on the challenge of developing porous metal arylphosphonates with both high crystallinity and functional porosity by using different synthetic approaches. Metal phosphonates are an extensive class of materials based upon extended inorganic-organic architectures such as chains, layers and three-dimensional networks. Metal phosphonates generally favor extended inorganic architectures leading to pillared materials with no porosity. We found that the use of template molecules, type of ligand and choice of metal ions could be used to deviate from the pillared structure. Many of these structures had interesting properties that were explored. The results can be divided into three areas: We developed non-pillared monovalent metal phosphonates by investigating both the role of water and template molecules in the solvothermal synthesis. The role of water in solvothermal reactions was found to have a profound influence on the structure of monovalent metal phosphonates and the structures could be tailored from zero/one-dimensional to two-dimensional. Non-pillared structures could be synthesized by using template molecules. For a zinc phosphonate, we converted a layered structure into a three-dimensional framework by using small template molecules in the solvothermal reaction. The compound exhibited reversible dehydration behavior. The change in the framework structure and guest positions was monitored during this process. Two different ligands were used in the development of porous aluminum phosphonates. One series exhibited reversible dehydration behavior, which had a dramatic influence on permanent porosity of the material. The stability of the dehydrated phase is a result of the geometry of the aluminum atom, which in some cases has coordinatively unsaturated metal sites. The second series was developed with ion exchange applications in mind therefore the pore environment was tailored to favor ion exchange processes. The most important aspect is that these compounds exhibit high selectivity for Th4+ ions. In total 28 new compounds were prepared, and their utility and structures clarified. The electronic version of this dissertation is accessible from http://hdl.handle.net/1969.1/151103

Metal Phosphates and Phosphonates

Metal Phosphates and Phosphonates PDF Author: Ram K. Gupta
Publisher: Springer Nature
ISBN: 3031270622
Category : Science
Languages : en
Pages : 401

Book Description
This book provides fundamental electrochemical behavior and understanding of devices based on Metal Phosphates and Phosphonates. The basic concepts, properties and emerging applications of these materials as batteries, supercapacitors, fuel cells, sensors, biomedical and environmental are covered. Apart from conventional techniques, this book explores new aspects of synthesizing Metal Phosphates and Phosphonates.

Chemistry and Application of H-Phosphonates

Chemistry and Application of H-Phosphonates PDF Author: Kolio D. Troev
Publisher: Elsevier
ISBN: 008047649X
Category : Science
Languages : en
Pages : 308

Book Description
Chemistry and Application of H-Phosphonates is an excellent source for those planning the synthesis of new phosphorus-containing compounds and in particular derivatives containing a phosphonate, phosphoramide or phosphonic acid diester group. The rich chemistry, low cost and easy availability of diesters of H-phosphonic acid makes them an excellent choice as synthone in a number of practically important reactions. Phosphonic acid esters are intermediates in the synthesis of important classes of compounds such as alpha-aminophosphonic acids, bisphosphonates, epoxyalkylphosphonates, alpha-hydroxyalkylphosphonates, phosphoramides, poly(alkylene H-phosphonate)s, poly(alkylene phosphate)s, nucleoside H-phosphonates. The synthesis of each of these compound classes is reviewed in detail. Alpha-Aminophosphonic acids are an important class of biologically active compounds, which have received an increasing amount of attention because they are considered to be structural analogues of the corresponding Alpha-amino acids. The utilities of alpha-aminophosphonates as peptide mimics, haptens of catalytic antibodies, enzyme inhibitors, inhibitors of cancers, tumours, viruses, antibiotics and pharmacologic agents are well documented. Alpha-Hydroxyalkanephosphonates are compounds of significant biological and medicinal applications. Dialkyl epoxyalkylphosphonates are of interest because of their use as intermediates in the synthesis of bioactive substances, and as modifiers of natural and synthetic polymers. Bisphosphonates are drugs that have been widely used in different bone diseases, and have recently been used successfully against many parasites. Poly(alkylene H-phosphonate)s and poly(alkylene phosphate)s are promising, biodegradable, water soluble, new polymer-carriers of drugs. Nucleoside H-phosphonates seem to be the most attractive candidates as starting materials in the chemical synthesis of DNA and RNA fragments. The 5’-hydrogen phosphonate-3’-azido-2’,3’-dideoxythimidine is one of the most significant anti-HIV prodrug, which is currently in clinical trials. Chapters review the synthesis; physical and spectral properties (1H, 13C, 31P and 17O NMR data); characteristic reactions; important classes of compounds based on these esters of H-phosphonic acid; their application as physiologically active substances, flame retardants, catalysts, heat and light stabilizers, lubricants, scale inhibitors, polymer-carriers of drugs; preparation of H-phosphonate diesters and general procedures for conducting the most important reactions. * provides ideas for the synthesis of phosphonates, phosphoramides and diesters of phosphonic acid (new phosphorus-containing compounds)* reviews structure, spectra and biological activity of H-phosphonates and their derivatives* examines new areas of application of phosphorus-containing compounds

Metal Phosphonates and Phosphinates

Metal Phosphonates and Phosphinates PDF Author: Ferdinando Costantino
Publisher:
ISBN: 9783039280032
Category : Mathematics
Languages : en
Pages : 120

Book Description


Crystalline Metal-Organic Frameworks Based on Conformationally Flexible Phosphonic Acids

Crystalline Metal-Organic Frameworks Based on Conformationally Flexible Phosphonic Acids PDF Author: Kevin James Gagnon
Publisher:
ISBN:
Category :
Languages : en
Pages :

Book Description
The goal of the work described in this dissertation was to investigate the structure of metal phosphonate frameworks which were composed of conformationally flexible ligands. This goal was achieved through investigating new syn-thetic techniques, systematically changing structural aspects (i.e. chain length), and conducting in situ X-ray diffraction experiments under non-ambient conditions. First, the use of ionic liquids in the synthesis of metal phosphonates was investigated. Reaction systems which had previously been studied in purely aqueous synthetic media were reinvestigated with the addition of a hydrophobic ionic liquid to the reaction. Second, the structural diversity of zinc alkylbisphosphonates was investigated through systematically varying the chain length and reaction conditions. Last, the structural changes associated with externally applied stimuli (namely temperature and pressure) on conformationally flexible metal phosphonates were investigated. Elevated temperature was used to investigate the structur-al changes of a 1-D cobalt chain compound through three stages of dehydration and also applied pressures of up to 10 GPa were used to probe the structural resilience of two zinc alkylbisphosphonate materials under. The iminobis(methylphosphonic acid) type ligands are a good example of a small, simple, conformationally flexible ligand. There are three distinct different structural types, utilizing this ligand with cobalt metal, described in the literature, all of which contain bound or solvated water molecules. The addition of a hydrophobic ionic liquid to an aqueous synthesis medium resulted in new anhydrous compounds with unique structural features. Systematic investigations of zinc alkylbisphosphonate materials, constructed with three to six carbon linker ligands, resulted in four new families of compounds. Each of these families has unique structural features which may prove interesting in future applications developments. Importantly, it is shown that whether the chain length is odd or even plays a role in structural type although it is not necessarily a requirement for a given structural type; furthermore, chain length itself is not strictly determinative of structural type. Dehydration in a cobalt phosphonate was followed via in situ single crystal X-ray diffraction. The compound goes through a two-stage dehydration mecha-nism in which the compound changes from a 1-D chain to a 2-D sheet. This pro-cess is reversible and shows unique switchable magnetic properties. The high pressure studies of an alkyl chain built zinc metal phosphonate showed that the chains provide a spring-like cushion to stabilize the compression of the system allowing for large distortions in the metal coordination environment, without destruction of the material. This intriguing observation raises questions as to whether or not these types of materials may play a role as a new class of piezo-functional solid-state materials. The electronic version of this dissertation is accessible from http://hdl.handle.net/1969.1/151137

Layered Metal Phosphonates as Templates for the Assembly of Ordered Molecular Systems

Layered Metal Phosphonates as Templates for the Assembly of Ordered Molecular Systems PDF Author: Mark R. Torgerson
Publisher:
ISBN:
Category : Chemical structure
Languages : en
Pages : 398

Book Description