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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
METAL-ORGANIC FRAMEWORKS WITH HETEROGENEOUS STRUCTURES A unique book that sheds light on Metal-Organic Frameworks complex systems that often display behaviors that surprise and cannot be easily described. In this book, MOF-based heterostructures technology with key characteristics is completely analyzed and the current state-of-the-art is discussed. The authors focus on the complex heterostructures promoted by MOFs with advantage of their recent new advances for various applications with particular emphasis on their design. As an extension of the design and synthesis, the shaping technology of heterostructure MOFs is also of great significance to the future practical applications in industry (adsorption/desorption, gas storage, catalysis, conductivity, optical activity) of this class of complex porous materials. As this unique book covers all of the aspects of complexity in MOFs with heterogeneous structures, it serves as an essential reference to the concepts of introducing complexity to designing the future new platforms of materials with advanced and superior properties. This important compact book provides the reader with: The principal aspects of heterogeneity that produce complexity in MOFs, their effects in the structure chemistry, performance and applications The effects of complexities on the structure of metal-organic frameworks The roles of complexities on metal-organic frameworks applications Explanation of synthesis strategies of the complex heterostructure MOFs. Audience This book will be beneficial for chemists, materials engineers, advanced postgraduate and graduate students, researchers and specialists who are working in the area of materials design and their chemistry, porous crystalline materials, coordination polymers, hybrid and functional materials, as well as industry professionals, such as those working on selective catalysis and adsorption-separation, optics, gas capture, processes of biological and pharmaceutical.
Flexible metal–organic frameworks (MOFs) are a unique class of porous materials that feature stimuli-responsive flexible structures and dynamic structural transformation behaviours. Exhibiting structural changes in response to physical or chemical stimuli creates related functions that can be developed for practical applications. The specific components and architectures of flexible MOFs are key to their unique properties, so understanding their chemistry is of critical importance for more targeted construction and functional research. This book provides an accessible overview of the historical background of the chemistry of flexible MOFs and their features; in particular, design and synthesis, dynamic structure analysis, flexibility, function and theoretical treatment, and interpretation of the mechanisms as well as their applications. It gives readers a fundamental understanding of this chemistry and will be of great help to young researchers, as well as those already familiar with conventional porous materials in creating new materials.
The series Topics in Current Chemistry Collections presents critical reviews from the journal Topics in Current Chemistry organized in topical volumes. The scope of coverage is all areas of chemical science including the interfaces with related disciplines such as biology, medicine and materials science. The goal of each thematic volume is to give the non-specialist reader, whether in academia or industry, a comprehensive insight into an area where new research is emerging which is of interest to a larger scientific audience.Each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years are presented using selected examples to illustrate the principles discussed. The coverage is not intended to be an exhaustive summary of the field or include large quantities of data, but should rather be conceptual, concentrating on the methodological thinking that will allow the non-specialist reader to understand the information presented. Contributions also offer an outlook on potential future developments in the field.
Metal–organic frameworks (MOFs) are porous crystalline polymers constructed by metal sites and organic building blocks. Since the discovery of MOFs in the 1990s, they have received tremendous research attention for various applications due to their high surface area, controllable morphology, tunable chemical properties, and multifunctionalities, including MOFs as precursors and self-sacrificing templates for synthesizing metal oxides, heteroatom-doped carbons, metal-atoms encapsulated carbons, and others. Thus, awareness and knowledge about MOFs and their derived nanomaterials with conceptual understanding are essential for the advanced material community. This breakthrough new volume aims to explore down-to-earth applications in fields such as biomedical, environmental, energy, and electronics. This book provides an overview of the structural and fundamental properties, synthesis strategies, and versatile applications of MOFs and their derived nanomaterials. It gives an updated and comprehensive account of the research in the field of MOFs and their derived nanomaterials. Whether as a reference for industry professionals and nanotechnologists or for use in the classroom for graduate and postgraduate students, faculty members, and research and development specialists working in the area of inorganic chemistry, materials science, and chemical engineering, this is a must-have for any library.
This title takes researchers in as well as out of the field of metal-organic framework (MOF) and then guides them on a journey to rediscover and rethink how these designer coordination polymers will influence the realm of materials science. This book opens with a look at a deeply controversial issue, MOF stability, which has plagued many systems, but ultimately has led to better materials that proved to be more robust allowing them to be investigated for multiple applications. This book successfully highlights many of these useful applications that MOFs are well adapted for. Because MOF components, inorganic and organic, can combine the best of both chemical domains, MOFs will improve our environment by removing harmful contaminants from the air and water, reduce the energy required to perform chemical reactions, partition hard to separate molecular mixtures, and form the next-generation of magnetic and electronic materials. MOFs will eventually be used for everyday activities — for monitoring or reacting to changing conditions. Readers of this book can then take note and implement MOFs in their line of research.
Metal Organic Frameworks: Fundamentals to Advanced offers a substantial and complete treatment of published results. The book includes a summary of current research, along with an in- depth explanation of Metal organic frameworks (MOFs) and applications in this versatile area. Metal organic frameworks (MOFs) are structured frameworks made up of metal ions and organic molecules. These materials are similar to sponges and can absorb, retain and remove molecules from their pores. As a result, metal-organic frameworks (MOFs) are the most rapidly evolving substances in chemistry with the highest surface areas due to their well-ordered pore structure.The exciting and vast surface area allows for more chemical reactions and molecule adsorption, hence this new resource provides the newest updates on the topics covered. Covers the synthetic advantages and versatile applications of metal-organic frameworks (MOFs) due to their organic-inorganic hybrid nature and unique porous structure Includes energy applications such as batteries, fuel storage, fuel cells, hydrogen evaluation reactions and super capacitors Features information on using MOFs as a replacement to conventional engineering materials as they are lightweight, less costly, environmentally-friendly and sustainable
Metal-organic frameworks (MOFs) are porous crystalline materials, consisting of inorganic metal nodes and organic linkers. These materials possess many merits, such as light weight, high specific surface areas, well-defined porosities and open site structures. The first chapter of this book focuses on the major breakthroughs of MOFs reported to date for nanomedicine applications followed by a short commentary addressing deficient areas in the field and the future direction of MOF based therapeutics. Chapter Two provides an overview of the current state of MOFs in solidphase microextraction (SPME) together with future expectations in the field. Chapter Three reviews the methods used to fabricate MOFs and discusses the use of MOFs in sensor development. The last chapter focuses on newly emerging MOFs, MOFs-supported and MOFs-derived materials. It discusses the recent progress of preparation and applications of these MOF-based materials in the electrocatalysis for oxygen reduction reaction (ORR) and/or oxygen evolution reaction (OER).
Some 80,000 metal-organic frameworks (MOFs) have been reported as of 2020. With intriguing structures and fascinating properties, MOFs are poised to be a defining material of the 21st century with a great deal of commercial potential from methane fuel automobile tanks to carbon capturing. Metal-Organic Frameworks provides an introduction to the complex world of MOFs. Researchers new to MOFs can use this work as a jumping-off point for theoretical study or applied research. The work is broad and expansive in scope, but inclusive and comprehensive in detail. The authors provide a personal perspective of MOF research that provides a strong foundation in the basic methods and themes as well as directs the reader in how to think about MOFs. Sixteen MOF structures are animated, providing more clarity into the dimensionality of MOFs. Accompanying links take the reader to additional 3-D structures provided by The Cambridge Crystallographic Data Centre (CCDC).