Coordination Polymers: Design, Analysis and Application - Hardcover

Batten, Stuart R.; Neville, Suzanne M.; Turner, David R.

Hardcover

ISBN 10: 0854048375 ISBN 13: 9780854048373

Verlag: Royal Society of Chemistry, 2009

Inhaltsangabe

Awarded the 2009 Olle Prize! The field of coordination polymer research has undergone rapid expansion in recent years. No longer are these materials the vaguely defined 'insoluble material' at the bottom of your vessel that spell death for your reaction. They have gone from 'polymeric rubbish' to 'materials of the future'. Great leaps in the deliberate design of coordination polymers were made in the 1990s. These were allied with similar advances in related areas such as organic crystal engineering, metallosupramolecular chemistry and X-ray diffraction. No longer did we assemble things atom by atom. Whole molecules were used as building blocks and new materials were made. This is the first book to provide a broad overview of all the major facets of coordination polymer research in one place. It combines chapters on nets and interpenetration with wide-ranging surveys of transition metal and lanthanoid coordination polymers and their properties. The aim is to provide a flavour of each aspect whilst introducing the important concepts and developments using carefully selected examples. After an introduction, the text is split into three sections: -Design (nets, interpenetration, malleability) -Analysis (transition metal coordination polymers, lanthanoid coordination polymers, organometallic networks, organic-inorganic hybrids) -Application (magnetic properties, porosity, acentric and chiral networks, reactive coordination polymers, other properties). Written in the style of a tutorial review, the book is suitable for both senior specialists and new postgraduate students taking their first steps in the field. It also provides an authoritative and detailed reference source.

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Über die Autorinnen und Autoren

Stuart R. Batten completed a BSc(Hons) and PhD at the University of Melbourne before taking up postdoctoral positions at the Universities of Bristol and Melbourne, and Monash University. He held two consecutive ARC fellowships at Monash, where he accepted a Lectureship and was subsequently promoted to Senior Lecturer in 2007. He has 150 publications to his name (mainly in the area of coordination polymers) and has been awarded numerous prizes for his work, including the Rennie, Edgeworth David and HG Andrewartha medals, and the Le FÞvre prize. Suzanne M. Neville completed a BSc(Hons) and PhD (on porous functional coordination polymers) at the University of Sydney. She currently holds a postdoctoral position at Monash University and has been awarded a Marie Curie Fellowship for 2008 to continue research into spin crossover materials at the ICMCB, Bordeaux. She has numerous publications to her name in the areas of coordination polymers and functional magnetic materials. David R. Turner completed a M.Sci. in Chemistry at King's College, London and a Ph.D. at King's College and Durham University. He currently holds an ARC post-doctoral fellowship at Monash University. Dr Turner is the author of 30 publications in the areas of supramolecular chemistry and crystal engineering and is a co-author of an undergraduate textbook on supramolecular chemistry and nanochemistry.

Stuart R. Batten completed a BSc(Hons) and PhD at the University of Melbourne before taking up postdoctoral positions at the Universities of Bristol and Melbourne, and Monash University. He held two consecutive ARC fellowships at Monash, where he accepted a Lectureship and was subsequently promoted to Senior Lecturer in 2007. He has 150 publications to his name (mainly in the area of coordination polymers) and has been awarded numerous prizes for his work, including the Rennie, Edgeworth David and HG Andrewartha medals, and the Le FÞvre prize. Suzanne M. Neville completed a BSc(Hons) and PhD (on porous functional coordination polymers) at the University of Sydney. She currently holds a postdoctoral position at Monash University and has been awarded a Marie Curie Fellowship for 2008 to continue research into spin crossover materials at the ICMCB, Bordeaux. She has numerous publications to her name in the areas of coordination polymers and functional magnetic materials. David R. Turner completed a M.Sci. in Chemistry at King's College, London and a Ph.D. at King's College and Durham University. He currently holds an ARC post-doctoral fellowship at Monash University. Dr Turner is the author of 30 publications in the areas of supramolecular chemistry and crystal engineering and is a co-author of an undergraduate textbook on supramolecular chemistry and nanochemistry.

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Coordination Polymers: Design, Analysis and Application is the first book to provide a broad overview of all the major facets of coordination polymer research in one place. It combines chapters on nets and interpenetration with wide-ranging surveys of transition metal and rare earth coordination polymers and their properties. The aim is to provide a flavour of each aspect of Cordination Polymers whilst introducing the important concepts and developments using carefully selected examples. After an introduction, the text is split into three sections: -Design (nets, interpenetration, malleability) -Analysis (transition metal coordination polymers, lanthanoid coordination polymers, rare earth coordination polymers, organometallic networks, organic-inorganic hybrids) -Application (magnetic properties, porosity, acentric and chiral networks, reactive coordination polymers, other properties). Written in the style of a tutorial review, the book is suitable for both senior specialists and new postgraduate students taking their first steps in the field. It also provides an authoritative and detailed reference source.

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Coordination Polymers

Design, Analysis and Application

By Stuart R. Batten, Suzanne M. Neville, David R. Turner

The Royal Society of Chemistry

Copyright © 2009 Stuart R. Batten, Suzanne M. Neville and David R. Turner
All rights reserved.

ISBN: 978-0-85404-837-3

Contents

Chapter 1 Introduction, 
Chapter 2 Nets: A Tool for Description and Design, 
Chapter 3 Interpenetration, 
Chapter 4 Malleability of Coordination Polymers, 
Chapter 5 Transition Metal Coordination Polymers, 
Chapter 6 Rare Earth Coordination Polymers, 
Chapter 7 Organometallic Networks, 
Chapter 8 Inorganic–Organic Hybrids, 
Chapter 9 Magnetism in Coordination Polymers, 
Chapter 10 Porous Coordination Polymers, 
Chapter 11 Acentric and Chiral Networks, 
Chapter 12 Reactive Coordination Polymers, 
Chapter 13 Other Properties of Coordination Polymers, 
Subject Index, 416, 

CHAPTER 1

Introduction

1.1 Introduction

Sometime between 1704 and 1705, a Berlin colourmaker named Diesbach made a mistake. He was trying to make a red pigment known as cochineal red lake. The recipe was simple – iron sulfate and potash. But it turned out pale. Upon further concentration, it became deep blue! By using cheap potash, contaminated with animal oil made from ox blood, Diesbach had created Prussian Blue. This was the first man-made coordination polymer and in fact the first man-made coordination compound. It was also a valuable pigment; within a few short years it was being made commercially from a closely guarded recipe.

It would, however, be another 372 years before the structure of Prussian Blue, Fe4[Fe(CN)6]3·x H2O, would be determined (Figure 1.1a). In the intervening years, little attention was paid to coordination polymers (certainly much less than their organic cousins received), with only a few scattered structural studies. The structures of Zn(CN)2 and Cd(CN)2 were reported by a Russian group in the depths of World War II. Powell and Rayner determined the structures of the Hofmann clathrate, [Ni(NH3)2Ni(CN) 4]·2C6H6, shortly afterwards (Figure 1.1b); this work was later extensively followed up by Iwamoto's group on related compounds. In 1959, a Japanese group reported, remarkably, that they had determined that the structure of [Cu(adiponi-trile)]NO3 contained six interpenetrating diamond networks. The ID chain structures of Ag(pyrazine)NO3 and Cu(pyrazine)(NO3)2 were reported in 1966 and 1970, respectively. The crystal structure of Co(pyrazine)2 Cl2 was shown to have a square grid structure in 1971.

As the 1980s came to a close, there was increasing interest in these materials, particularly in the field of molecule-based magnetic materials. However, it was not until a short communication in 1989, and a subsequent full paper in 1990, that interest really took off.

In these and subsequent papers, Robson, Hoskins and co-workers outlined a net-based approach to the design of coordination polymers. They took the landmark work of Wells, which described crystal structures in terms of networks, and applied it to the design of new coordination polymers (Figure 1.2). Through this design approach, they proposed that new materials with interesting properties such as porosity and catalysis could be deliberately engineered. These ideas soon caught on, with other early groups in the field making important contributions that would ultimately lead to the explosion in research illustrated in Figure 1.3.

1.2 Crystal Engineering, Supramolecular Chemistry, Metallosupramolecules

The development of coordination polymer research was reinforced by the growth of two other closely related areas: crystal engineering and supramolecular chemistry (particularly metallosupramolecular chemistry).

Crystal engineering seeks to understand why molecules pack in the ways that they do and to use that knowledge to deliberately engineer the arrangements of molecules in new materials. This is important because the properties of materials are often governed by the way in which their constituent molecules are arranged. Control over this arrangement gives control over the properties.

In 'molecular' (largely organic) crystal engineering, the interactions are weaker than coordination bonds and can range in strength from very strong hydrogen bonding to weak C–H ··· A hydrogen bonds, halogen bonds, π interactions and, ultimately, van der Waals forces. The crystal engineer seeks to understand and harness all these interactions. However, despite the differences in the interactions, there is much that is common in these two areas. Indeed, coordination polymers, which essentially exist only in the solid state, should be considered as a subset of crystal engineering. Furthermore, the net-based approach for coordination polymers is equally valid for molecular species connected by well-defined interactions. For example, trimesic acid (benzene-1,3, 5-tricarboxylic acid) readily forms hexagonal sheets in which the molecules are connected by hydrogen bonding, as shown in Figure 1.4a. The large organic molecule shown in Figure 1.4b assembles, as one would predict, into seven interpenetrating diamond networks through hydrogen bonding between the peripheral functional groups.

Many of the concepts and terminology in molecular crystal engineering also apply to coordination polymers. Interactions between molecules that direct their packing arrangements (such as the hydrogen bonding carboxylate dimer motif in Figure 1.4a) are known as supramolecular synthons; in coordination polymers, the main synthons are coordination bonds (although weaker synthons can also be important, as discussed in Chapter 4). The building blocks used to create the structure, such as the molecules shown in Figure 1.4, are called tectons; for coordination polymers, the tectons are metal ions and ligands. These two concepts are highlighted in Figure 1.5.

The aim of supramolecular chemistry is similar: to create assemblies of molecules, that is, not to create structures an atom at a time, but to design molecules such that when combined they spontaneously self-assemble in a predetermined fashion into larger architectures. Thus crystal engineering can, in fact, be considered to be the supramolecular chemistry of the solid state. To quote Dunitz, 'The crystal is, in a sense, the supramolecule par excellence ...'.

The supramolecular chemist, like the crystal engineer, uses a range non-covalent intermolecular interactions, including hydrogen bonding and coordination bonds. Use of the later gives rise to metallosupramolecular chemistry, and much of the design and indeed the structures obtained have close relationships to coordination polymers. For example, the design and chemistry may be similar, except that the use of a convergent ligand building block will give a metallosupramolecule whereas a divergent one will generate a polymer (Figure 1.6a). Alternatively, even the same bridging ligand can be used, with construction of a metallosupramolecule being directed by the use of 'capping' chelating co-ligands on the metals [such as 2,2'-bipyridine, ethy-lenediamine (en), 1,10-phenanthroline, 1,4,7-triazacyclononane (TACN), cyclopentadiene]. In the absence of these capping groups, polymers are formed (Figure 1.6b). Despite the different products, both areas have the same modular approach to the design and synthesis and similar (or even the same) building blocks.

Even the architectures achieved in the two fields can be...

Details zur Ausgabe

• Verlag: Royal Society of Chemistry
• Erscheinungsdatum: 2009
• Sprache: Englisch
• ISBN 10: 0854048375
• ISBN 13: 9780854048373
• Einband: Gebundene Ausgabe
• Anzahl der Seiten: 424
• Kontakt zum Hersteller: Nicht verfügbar
• Verantwortliche Person: preigu; mail@preigu.de; ; Lengericher Landstr. 19; Osnabrück; 49078; Deutschland