Comprehensive Supramolecular Chemistry – serie

In the present volume, an effort has been made to organize and present a comprehensive overview of receptors for cationic guests. This begins with reviews of the various basic complexing systems: podands, crown ethers, lariat ethers, cryptands, and spherands. Natural cation-binding agents are also important hosts in supramolecular chemistry and their chemistry has been extensively studied. The structural aspects of complexation by natural hosts and crown ethers are reviewed separately and the topic is addressed for specific receptor systems within chapters dedicated to specific hosts. The physical chemistry of complexation and transport is reviewed along with the important application of anion activation, sometimes called phase-transfer catalysis. In the second dozen or so chapters are presented overviews of specialized areas such as the formation of alkalides, the development of chemical sensors, chromoionophores, and redox-switchable receptors. The volume concludes with discussions of transition metal complexes of macrocyclic ligands, second-sphere coordination, complexes of organometallics, and finally of fullerenes.

This second volume, containing 18 chapters, is devoted to the design, synthesis and complexingability for molecular guest substances of the presently known synthetic host compounds.Uncharged organic molecules, cations and anions are the targets to be selectively complexed,imprisoned, transported and extracted. The first chapters provide a more general introductioninto macrocycle synthesis and well known examples of complementary host/guest structures aswell as into the supramolecular binding types. The following chapters consequently givedetailed insight into the hitherto known synthetic receptor substances of all kinds (includingcrown compounds, calixarenes, carcerands, siderophores etc) and their selective interaction withfitting molecular guest substrates.This volume contains many structural and host/guest illustrations including colouredillustrations, and also refers to other volumes of this series with regard to, for example, templatesynthesis, catenanes, analytical applications etc.

The total number of papers, conferences, abstracts and patents dedicated to cyclodextrins by the end of 1995 will be about 12,000 in number. This vast number of publications deals with the chemistry (structure, chemical reactivity), biology (enzymology, metabolism, toxicity, direct therapeutic effects), inclusion complex forming capacity and its consequences, and industrial utilization of cyclodextrins (in drugs, foods, cosmetics, chromatography, catalysis biotechnology, diagnostics etc) in unlimited numbers of products and technologies.This volume pulls all this information together, covering the chemistry, biology and industrial application of cyclodextrins as molecular encapsulating agents in research methods, analytical procedures, industrial technologies and products.

This volume containing 15 chapters is practically classified into four parts. Part 1 deals with rapidly growing areas in bioorganic chemistry, covering antibody catalysis, structural aspects of DNA and DNA binding agents and protein mimetics. Part 2 describes receptor functions in relation to biochemical phenomena. Part 3 involves biomimetic reactions covering electron and energy transfer in supramolecular model systems, metalloporphyrin catalysis, zinc enzyme models and artificial enzymes with Vitamin B6 and B12 activity. Some aspects of enzyme chemistry are described in Part 4, covering kinetic, thermodynamic and supramolecular aspects of enzyme catalysis and site-directed mutagenesis of proteins.

In this volume, an overview of the expanse of bioinorganic systems that involve supramolecular chemistry has been assembled. It commences with introductions to the supramolecular aspects of bioinorganic synthetic analogues and of metalloprotein structure and function. From there, a range of topics involving diverse metallobiomolecules (proteins, nucleic acids, and their synthetic analogues) are developed.

This volume, containing 27 chapters, provides a state-of-the-art account of the chemistry of solid-state supramolecular systems. Following a valuable introductory chapter reviewing important general principles, the coherent coverage is structured in the form of a series ofcontributions all written by experts in the respective areas comprehensively described. Throughout the volume, emphasis is placed not only on the design and structure of new hostsystems but also on practical applications of these novel materials in real chemical situations. The crystal engineering methods described relate to the synthesis of both organic and inorganictailor-made hosts. Also the reader is presented with highly relevant descriptions ofthermodynamic and kinetic considerations germane to the formation crystalline inclusioncompounds. The final chapter gives a fascinating account of the self-organisation of moleculesin two and three dimensions, crucially important to any process of crystal nucleation.

Supramolecular chemistry in inorganic hosts is treated in two parts in this Volume. The first part focuses on layered solids and their intercalation chemistry, the second on molecular sieves and zeolites. In the first part, after a preliminary chapter on typical behavior and general properties of twodimensional solids, the structural aspects and the chemistry of specific classes of layered solids, including graphite intercalation compounds, layered metal chalcogenides, phosphates, phosphonates, clays, layered double hydroxides and layered perovskites are treated. Attention is given to intercalation reactions and pillared solids with open porosity, including covalently pillared materials. Additional chapters deal with special topics such as film growth of layered materials, exfoliation reactions, photochemistry/electron transfer and ionic conductivity. In the second part, after discussing structural aspects of molecular sieves, the volume treats the multitude of synthetic strategies and current theories about hydrothermal synthesis mechanisms, followed by a discussion of molecular interactions with micropore hosts. Aspects of adsorption, molecular dynamics and diffusion are developed, and specific examples of inclusion chemistry are covered, including metal clusters in zeolites, and intrazeolite synthesis of organometallic complexes. The reactivity of molecules in micropore hosts, and relevant applications of molecular sieves are discussed in chapters on molecular shape selectivity in hydrocarbon catalysis, oxidation reactions, supramolecular photochemistry in zeolites, and novel materials such as sensors, membranes, and nonlinear optical effects in intrazeolite assemblies.

The characterization of supramolecular compounds in terms of their stoichiometry, structure and binding properties is a necessary pre-requisite to the understanding of their remarkable selectivity towards guests. The diversity of systems covered by the term "supramolecular" requires the use of an extremely varied range of physical techniques. This volume gives detailedcoverage of the physical methods used, reporting not only on the results but also outlining the theoretical and experimental aspects for each technique.

Volume 9 contains 18 chapters devoted to recent developments in the field of template reactionsand self-assembly or self-organization processes.A large variety of approaches is described, spanning transition metal-based template strategiesallowing to build more and more complex and functionalized structures, to purely organicprocedures. The latter methodology has been applied to the construction of topologicallyfascinating systems as well as to organized assemblies (biomimetic materials, mesaphases, etc)with well defined structures and specific properties.

In this last volume of the set, a state-of-the-art overview of (future) supramolecular technology and its current applications is given, but without attempting to cover all possible emerging new technologies.

In the first part of this volume (Chapters 1-6) separation technologies based on selective molecular recognition are dealt with. The transduction of a chemical recognition phenomenon into a measurable signal is discussed in Chapters 7-10.

The next section covers the area of supramolecular reactivity. The design of molecules that will fit the transition state of a chemical reaction is one of the major challenges in supramolecular chemistry. This stabilization leads to catalysis. Related to this topic are the contents of Chapters 12-14 where the activation of reactive anions by complexation of the cation, phase-transfer catalysis, and the storage of reagents are reviewed. Medical applications such as drug delivery from, or imaging and targeting by, supramolecular systems are described in Chapters 16 and 17.

The last part of this volume covers different material properties ranging from inclusion polymerization to nonlinear optical materials.