The authors of this volume concentrate on the recent progress of novel polyoxometalate (POM) syntheses, as well as advances made in catalytic, electrochemical, and sensing systems. The state-of-the-art techniques such as flow system and gel-electrophoresis for the discovery of POMs are covered with a detailed discussion. Of particular importance, the application of POM-based materials in photo-sensing, heterogeneous catalysis, energy conservation and storage, and gas separation is reviewed. Over the past few years, POM chemistry has witnessed a remarkable progress with more than 1500 papers published each year. Due to their intrinsic structural features, POMs are considered as versatile building blocks for the construction of sophisticated complex assemblies and advanced multi-functional materials. Various strategies, methods, and techniques have been adopted to develop POM-based materials with intriguing properties and excellent performance. All the contributors to this volume are young, vibrant chemists in this research field and all the works are carefully collected from the authors’ years of experience. This volume serves as an essential reference for every POM chemist and is of great interest to new researchers who wish to learn more about this area.
Polyoxometalates are anionic metal-oxo nanoclusters, which constitute a unique class of compounds owing to their rich solution equilibria and their unique compositional, electronic, reactive, and structural diversity. This book reviews metal-oxide cluster chemistry by covering topics ranging from fundamental aspects (i.e., structure, properties, self-assembly processes, derivatization) to functional materials that incorporate these molecular units, as well as their applications in the fields of current socioeconomic interest, such as energy storage systems, catalysis, molecular electronics, and biomedicine. Edited by prominent researchers in the field of polymer and polyoxometalate chemistries, the book compiles contributions from some of the most distinguished and promising scientists worldwide in such a way that it will appeal to a general readership involved in research areas related to chemistry and materials science.
This book focuses on modern coordination chemistry, covering porous coordination polymers, metalloproteins, metallopeptides, nanoclusters, nanocapsules, aligned polymers, and fullerenes. As well, it deals with applications to electronic devices and surface characterization. These wide-ranging topics are integrally described from the perspectives of dimensionality (one-, two-, and three-dimension), new materials design, synthesis, molecular assembly, function and application. The nine chapters making up this book have been authored by scientists who are at the cutting edge of research in this particular field. The level is appropriate for graduate students, post-doc researchers, and new faculty members whose aim is to become familiar with modern coordination chemistry from its basics to applications.
The work presented in this thesis highlights the influence of water soluble tertiary amines in the synthesis of transition metal substituted heteropolyoxometalates (TMSPs), with particular emphasis on polyanions based on the Keggin structure and lacunary derivatives thereof. In particular, an understanding is gained into the role that N,N'-bis(2-hydroxyethyl)piperazine (bhep) and morpholine (morph) play in the polyanion self-assembly process, with the successful isolation of molecular species, chains, layers and three dimensional frameworks. Each of the ligands were used in two different sets of synthetic investigation to probe their influence on the complete self-assembly of transition metal substituted tungstophosphates using Na2WO4 as the tungstate source, and by using the [XW10O36]8- X = Si, Ge precursors. Indeed, at no point in this work has the same polyanion been isolated using both the bhep and morpholine ligands, with this observation being indicative of each ligand having structure directing properties. Synthesis of TMSPs based on the phosphotungstate clusters in the presence of (bhep) has resulted in the isolation of clusters with nuclearities {W6}, {W7}, {W9}, {W10}, and {W11} which were only possible through fine control of the reaction pH which is aided by the ligands high buffer capacity. Additionally, in these compounds the ligand is observed to adopt a variety of coordination tendencies ranging from monodentate coordination through the ligands hydroxyl groups to chelation between nitrogen and oxygen donors. Specifically, the chelation of the ligand to CoII and NiII ions has allowed the rare inclusion of transition metal complexes into lacunary polyanions through a complimentary self-assembly process. Furthermore, the (bhep) ligand has been used to directly functionalise the [[gamma]-SiW10O36]8- polyanion through the controlled formation of W-OC linkages via a dehydration process. Interactions of the Morpholine ligand with heteropolytungsate clusters and transition metals in aqueous solution results in an array of markedly different structural motifs, which are highly depedant on the synthetic approach. The high basicity of the morpholine ligand results in its function as a buffer and cation within a pH domain that is underdeveloped in TMSP chemistry. Consequently, novel molecular species and functional materials have been isolated through the exploitation of this knowledge. The most significant of all the findings is the isolation of five mesoporous frameworks, which are composed solely of manganese or cobalt substituted Keggin polyanions which act as trigonal and tetrahedral nodes in the purely inorganic frameworks. Furthermore, the manganese containing frameworks have been shown to have cation exchange properties and are also redox active with single-crystal to single-crystal transformations being observed.
Polyoxometalate-Based Materials and Applications focuses on the recent progress in polyoxometalate-based materials for various electrochemical and biomedical applications. First, the structure, composition, classification, and properties of POMs-based materials are introduced. Then, their design for energy applications such as supercapacitors, batteries, hydrogen production are discussed. Finally, their use in biomedical (antibacterial, antiviral, cancer prevention/treatment) and sensing applications are reviewed. Polyoxometalate-based Materials and Applications is suitable for materials scientists and engineers, chemists, and chemical engineers.
This work incorporates contributions from polyoxometalate scientists, and presents a summary of research developments in this field. Topics discussed include synthetic strategies leading to functionalized organic polyoxometalate derivatives, oxothioanions, and supramolecular assemblies.
Large, hydrophilic polyoxoanions with high solubility in water and/or other polar solvents demonstrate unique solution behavior by self-assembling into single layer, hollow, spherical "blackberry"-like structures, which are obviously different from small, simple ions. These macroions cannot be treated as insoluble colloidal suspensions either because they form stable "real solutions". These inorganic macroions demonstrate some features usually Pobelieved to belong only to complex biological molecules, such as the self-recognition, chiral recognition, and chiral selection in dilute solutions. Highly negatively-charged molecular rods with almost identical structures were observed to self-assemble into their individual 'blackberry' structures, demonstrating tiny differences (e.g. charge, charge distribution, and organic ligands) could lead to self-recognition behavior. Chiral recognition behavior was understood by studying the self-assembly process in the racemic mixture solutions. Moreover, chiral organic molecules (lactic acid and tartaric acid) can be used to selectively inhibit the self-assembly process of one of the enantiomers. Meanwhile, polyoxometalate-based organic-inorganic hybrid materials demonstrate amphiphilic properties by self-assembling into vesicles and reverse vesicles in polar and non-polar solvents, respectively, and form catalytic emulsions in biphasic environments. Designed hybrid molecules can be programed to different devices with applications in fluorescence, photo-electronic conversion, molecular switch, and catalyst.
Smart materials constructed through supramolecular assemblies have been receiving considerable attention because of their potential applications, which include self-healing materials, energy storage, photonic devices, sensors and theranostics. Host–guest chemistry of various macrocyclic receptors with organic guests provides a unique way to control tailor-made nanoarchitectures for the formation of pre-designed functional materials. Cucurbituril-based Function Materials provides an overview of this fascinating macrocycle, cucurbituril (CB) homologues and derivatives-based supramolecular nanostructured materials. Chapters cover the synthesis, properties and application of CB-based smart materials and nanostructures. With contributions from key researchers, this book will be of interest to students and researchers working in materials science, as well as those working on cucurbituril-based materials in organic and physical chemistry.
There is great interest in metallosupramolecular materials because of their use in magnetic, photonic and electronic materials. Functional Metallosupramolecular Materials focuses on the applications of these materials covering the chemistry underlying the synthesis of a variety of ligands to coordinate various metal ions and the generation of 2D and 3D materials based on these constructs. The book starts by looking at different metallosupramolecular systems including naturally occurring functional metallosupramolecular materials; DNA-based metallosupramolecular materials; metallopolymers; metallogels as well as functional materials based on MOFs. Subsequent chapters then systematically cover the different applications such as molecular computation, spin-crossover, light harvesting and as photocatalysts for the production of solar fuels. The book provides an overview of functional metallosupramolecular materials that will be of interest to graduate students, academics and industrial chemists interested in supramolecular chemistry, materials science and the materials applications.
