[Truncated abstract] Chapter 1 provides an introduction to the 'sarcophagine' class of ligands and the field of metallopolymers. The synthesis, stereochemistry, physical properties and functionalisation of 'sarcophagines' and their metal complexes are discussed. A brief overview of the burgeoning field of metallopolymers is given with specific mention of the synthetic routes to pendant metallopolymers, and how these could be employed to prepared cage amine containing metallopolymers. Chapter 2 deals with the synthesis, characterisation and reactivity of cinnamylamino and styrylamido derivatives of the cage amines [Co((NH2)2sar)]3+, [Co((CH3)(NH2)sar)]3+ and [Cu((NH2)2sar)]2+. The cinnamylamino derivatives were prepared using reductive alkylation of the aforementioned amines with cinnamaldehyde. Procedures were developed to isolate the complexes without causing unwanted additions to the double bond. The cinnamylamino derivatives displayed unexpected reactivity towards a range of reducing agents, resulting in unexpected reduction of the double bond and cleavage of the cinnamyl group, but ultimately in the preparation of phenylpropylamino derivatives of [Co((NH2)2sar)]3+ and [Co((CH3)(NH2)sar)]3+. Attempts to rationalise the reactivity of the double bond have been explored based upon the physical properties and reactivity of the double bond. The styrylamido derivatives were prepared by treatment of the cage amines with 4-vinylbenzoyl chloride, and the complexes isolated in a similar manner to those of the cinnamylamino derivatives to ensure the amide linkage remained intact. Most of the complexes have been structurally characterised. ... Both the 2-thienyl and 3-thienyl derivatives of [Co((NH2)2sar)]3+ and [Co((CH3)(NH2)sar)]3+ have been prepared using reductive alkylation with the respective carboxaldehydes of thiophene. One of the optically pure isomers has been prepared. The complexes have been fully characterised including structural characterisation. Polymerisation of the thiophene-cage amine complexes was investigated under a range of chemical and electrochemical conditions, though polymerisation was never observed. Cleavage of the thienyl groups was observed when ceric ammonium nitrate in nitric acid was used as the oxidant. The attachment of oligothiophenes and mixed pyrrole-thiophene oligomers to cage amines were investigated using reductive alkylation and various pyrrole ring-forming reactions about the apical amino groups, though none of the desired complexes were isolated, reasons for the lack of reactivity were discussed. An efficient synthesis of N-(4-benzoic acid)- 2,5-di(2-thienyl)pyrrole was developed and was shown to the electropolymerisable, albeit the polymer films were non-conducting. Attempts to couple N-(4-benzoic acid)- 2,5-di(2-thienyl)pyrrole with a cage amine via its acid chloride were complicated by decomposition reactions, the nature of one of these products is discussed. Chapter 5 presents investigations into the preparation of simple complexes containing multiple cage amines using alkylation and acylation procedures with aromatic substrates. The complexes were found to exhibit some interesting electrochemical and chemical properties, demonstrating that even simple multiple cage amine species can display complicated and interesting behaviour.

Chapter 1 contains an Introduction to the role of metal complexes in functional assemblies. The remainder of the chapter is devoted to an Introduction to the "sarcophagine" class of ligands, including their synthesis, stereochemistry and electrochemical properties. Chapter 2 describes the synthesis of a variety of alkylated derivatives of the cage amines "diaminosarcophagine" and "aminomethylsarcophagine". Procedures have been developed for the selective functionalisation of the primary amine sites through protection of the secondary amines by coordination to a metal ion. Experiments with the Cu(II) complex of diaminosarcophagine indicated mono-, di-, and tri-alkylation were possible by varying the reaction conditions but separation of the various alkylation products was extremely difficult. Methods were developed, therefore, to prepare the desired di-alkylated products in a selective manner which overcame the need for difficult and tedious separations. A method for the isolation of the free aminomethylsarcophagine ligand in good yields was developed. Copper and magnesium complexes of this ligand were prepared, which allowed the selective synthesis of monoalkylated cages. Magnesium(II) complexes were employed to successfully protect the secondary amines, and allowed the ready removal of the metal ion from the cage to give the free alkylated ligands. These ligands could then be used to prepare a variety of metal complexes containing one or two alkyl groups. Chapter 3 describes attempts to prepare thermotropic metallomesogens (liquid crystals) of a variety of cage complexes. The simple mono- and di-alkylated compounds described in Chapter 2 were shown not to form thermotropic LC phases and new complexes containing three and six alkyl groups were prepared in the hope of producing mesogenic behaviour. None of the compounds synthesised exhibited thermotropic liquid crystalline phases but the aqueous solution behaviour of the triple tailed complexes displayed interesting phenomena, most notably the production of viscoelastic solutions at ≤ 1 wt%. This behaviour was shown, in the case of the Co(III) complex, to be due to the presence of long cylindrical or "wormlike" micelles in pure water, which can be readily converted to vesicle structures. The electrochemical behaviour of the Co(III) complex displayed some interesting adsorption behaviour at a hydrophobic electrode surface giving an immobilised film. Chapter 4 describes the synthesis and characterisation of a series of Co(III) complexes linked by short peptide-like disulfide spacers. The solution electrochemical characteristics of the new complexes is reported. Two immobilisation methods, namely electrodeposition and traditional "self-assembly", were investigated for the preparation of monolayers of the disulfides on gold surfaces and both were found to give indistinguishable equilibrium surface coverages and electrochemical characteristics. An initial induction period was observed, most evident for the electrodeposited films, and this phenomenon has been tentatively assigned as due to a surface rearrangement effect.

This fundamental book presents the most comprehensive summary of the current state in chemistry of cage metal complexes. After their previous book “The Encapsulation Phenomenon” (www.springer.com/978-3-319-27737-0) the authors in this book focus on the encapsulation of metal ions by different types of three-dimensional mono- and polynucleating caging ligands. Within these cage metal complexes, (metal) ions can be isolated from external factors. The book provides both a classification of the cage compounds and summaries of synthetic approaches. On that basis the authors then describe the unique chemical and physical properties and the resulting reactivity of the cage compounds, as well as practical and potential applications as potent topological drugs and prodrugs, antifibrillogenic agents, radiodiagnostic and radiotherapeutic compounds, paramagnetic probes, single-molecule magnets, electrocatalysts for hydrogen production, (photo)electronic devices, and many more. Readers will find a well-structured and concise overview, with particular emphasis on a review of synthesis and reactivity of various cage metal complexes, summarizing over 400 literature references, clearly presented in over 300 color schemes and figures.

- Microporous Organic Polymers: Design, Synthesis, and Function By J.-X. Jiang and A. I. Cooper - Hydrogen, Methane and Carbon Dioxide Adsorption in Metal-Organic Framework Materials By X. Lin, N. R. Champness, and M. Schröder -Doping of Metal-Organic Frameworks with Functional Guest Molecules and Nanoparticles By F. Schröder and R. A. Fischer -Chiral Metal-Organic Porous Materials: Synthetic Strategies and Applications in Chiral Separation and Catalysis By K. Kim, M. Banerjee, M. Yoon, and S. Das -Controlled Polymerization by Incarceration of Monomers in Nanochannels By T. Uemura and S. Kitagawa -Designing Metal-Organic Frameworks for Catalytic Applications L. Ma and W. Lin -Magnetic and Porous Molecule-Based Materials By N. Roques, V. Mugnaini, and J. Veciana

Comprehensive Supramolecular Chemistry II, Second Edition, Nine Volume Set is a ‘one-stop shop’ that covers supramolecular chemistry, a field that originated from the work of researchers in organic, inorganic and physical chemistry, with some biological influence. The original edition was structured to reflect, in part, the origin of the field. However, in the past two decades, the field has changed a great deal as reflected in this new work that covers the general principles of supramolecular chemistry and molecular recognition, experimental and computational methods in supramolecular chemistry, supramolecular receptors, dynamic supramolecular chemistry, supramolecular engineering, crystallographic (engineered) assemblies, sensors, imaging agents, devices and the latest in nanotechnology. Each section begins with an introduction by an expert in the field, who offers an initial perspective on the development of the field. Each article begins with outlining basic concepts before moving on to more advanced material. Contains content that begins with the basics before moving on to more complex concepts, making it suitable for advanced undergraduates as well as academic researchers Focuses on application of the theory in practice, with particular focus on areas that have gained increasing importance in the 21st century, including nanomedicine, nanotechnology and medicinal chemistry Fully rewritten to make a completely up-to-date reference work that covers all the major advances that have taken place since the First Edition published in 1996

Interest in nanoporous crystals as host-guest systems has risen dramatically over the past few years, such that this fascinating class of substances now plays an important role not only in material sciences, but also in numerous other disciplines, such as organic or supramolecular chemistry. With their unique characteristics, nanoporous crystals offer a wide range of possible applications: They are used as molecular sieves or membranes as well as catalytic converters. This work presents the very first overview of this exciting field. Readers will find everything they need to know about these unusual materials, with all their many attributes: · Synthesis of host-guest systems · Description of the structural and dynamic aspects · Electronic and optical characteristics of the materials · Possible applications. An indispensable reference for materials scientists as well as for catalytic and inorganic chemists, and all those working in the field.