Coordination Polymers

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

• ISBN13: 9780854048373
• ISBN10: 0854048375
• Format: Hardcover
• Copyright: 2009-02-01
• Publisher: Royal Society of Chemistry

Summary

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.

Table of Contents

Introduction
Introduction	p. 1
Crystal Engineering, Supramolecular Chemistry, Metallosupramolecules	p. 4
What is a Coordination Polymer?	p. 6
Synthetic Techniques	p. 10
Design, Analysis, Application	p. 12
References	p. 13
Nets: A Tool for Description and Design
Introduction	p. 19
Defining Networks	p. 20
Identifying and Naming Nets	p. 25
1D Nets	p. 28
2D Nets	p. 29
Common 3D Nets	p. 36
3-Connected Nets	p. 36
4-Connected Nets	p. 39
5-Connected Nets	p. 45
6-Connected Nets	p. 46
Higher Connected Nets	p. 47
Mixed Connectivity Nets	p. 48
Rod Packings	p. 52
References	p. 53
Interpenetration
Introduction	p. 59
Nomenclature	p. 67
1D Interpenetration	p. 69
2D Interpenetration	p. 70
3D Interpenetration	p. 77
Interpenetration of Nets of Different Composition, Topology and Dimensions	p. 84
Self-penetration	p. 87
Other Entangled Systems	p. 89
References	p. 89
Malleability of Coordination Polymers
Introduction	p. 96
Supramolecular Isomerism	p. 98
Malleability of Building Blocks	p. 107
Synthetic Approach	p. 111
Solvent Effects	p. 115
Other Guests	p. 119
Counterions	p. 120
Weaker Interactions	p. 124
Conclusion	p. 134
References	p. 134
Transition Metal Coordination Polymers
Introduction	p. 144
Pseudohalide Ligands	p. 146
The Cyanide Ligand	p. 146
The Azide Ligand	p. 149
NCX Ligands (X = O, S, Se)	p. 152
Small Polynitrile Ligands (e.g. dca/tcm)	p. 153
Larger Nitrile Donor Ligands	p. 156
Neutral Ligands	p. 156
Anionic Nitrile Ligands	p. 158
Pyridyl Donor Ligands	p. 159
2-Connecting Ligands	p. 159
3-Connecting Ligands	p. 164
4-Connecting Ligands	p. 165
Five-membered Ring Nitrogen Donor Ligands	p. 166
2-Connecting Ligands	p. 167
3-Connecting Ligands	p. 169
Other Connectors	p. 170
N-Oxide Ligands	p. 170
Carboxylate Ligands	p. 172
2-Connecting Ligands	p. 173
3-Connecting Ligands	p. 175
4-Connecting Ligands	p. 177
Other Ligands	p. 178
Mixed Donor Atom Ligands	p. 180
Mixed Ligand Coordination Polymers	p. 181
References	p. 183
Rare Earth Coordination Polymers
Introduction	p. 191
Cyanide/Nitrile and Pseudohalide Ligands	p. 192
Five-membered Ring Donors	p. 195
Pyridyl Donor Ligands	p. 196
N-Oxide Donors	p. 196
Rare Earth-Carboxylate Polymers	p. 202
Monocarboxylate Ligands	p. 203
Dicarboxylate Ligands	p. 205
Tricarboxylate Ligands	p. 210
Tetracarboxylate Ligands	p. 212
Other Ligands	p. 212
Oxalate Coordination Polymers	p. 212
Chloranilic Acid and Dihydroxybenzoquinone	p. 215
Polymers with Sufonate-containing Ligands	p. 217
Amide Ligands	p. 217
Pyridylcarboxylate Ligands	p. 219
Mixed 3d/4f Coordination Polymers	p. 221
Cyanide-based Bimetallic Polymers	p. 221
Carboxylate-based Bimetallic Polymers	p. 224
Pyridylcarboxylate Ligands	p. 224
Other Mixed O/N Donor Ligands	p. 229
Actinide Coordination Polymers	p. 229
References	p. 231
Organometallic Networks
Introduction	p. 238
Large Aromatic Ligands	p. 239
Cation-[pi] Interactions in Ag(1)-PAH Systems	p. 239
Cation-[pi] Interactions with Cyclophanes	p. 241
Non-aromatic Cation-[pi] Interactions	p. 243
Organometallic Complexes as Ligands	p. 245
Metallocene Bridging Ligands	p. 245
Metal-Quinone Bridging Complexes	p. 246
Isocarbonyl Polymers	p. 248
R[subscript 3]Sn/R[subscript 3]Pb Systems	p. 251
Metal-Cyanide Polymers	p. 251
(Triorganostannyl)tetrazole Polymers	p. 252
References	p. 254
Inorganic-Organic Hybrids
Introduction	p. 257
0D Metal-Oxide Substructures	p. 259
1D Metal-Oxide Substructures	p. 260
2D Polymers with 1D Metal-Oxide Substructures	p. 261
3D Polymers with 1D Metal-Oxide Substructures	p. 263
2D Metal-Oxide Substructures (Pillared Layers)	p. 264
References	p. 271
Magnetism in Coordination Polymers
Introduction	p. 273
Long-range Magnetic Ordering	p. 273
Introduction	p. 273
Molecule-based Magnets	p. 275
Single-chain Magnets	p. 293
Spin Crossover	p. 295
Introduction	p. 295
Five-membered Heterocyclic Ring Bridging Ligands	p. 297
Six-membered Ring Bridging Ligands	p. 301
Cyanide Bridges in Hofmann Phases	p. 305
References	p. 307
Porous Coordination Polymers
Introduction	p. 313
Terminology	p. 313
Designing Permanent Porosity	p. 315
Flexible Porosity	p. 317
Rigid Porosity	p. 322
Solvent Exchange	p. 326
Flexible Guest Exchange	p. 327
Rigid Guest Exchange	p. 329
Gas Storage	p. 330
Hydrogen Gas Storage	p. 331
Methane Gas Storage	p. 335
Carbon Dioxide Gas Storage	p. 336
Other Gases	p. 337
Ion Exchange	p. 338
Multifunctional Porous Materials	p. 338
Conclusion	p. 340
References	p. 341
Acentric and Chiral Networks
Introduction	p. 345
Acentric Networks for Non-linear Optical Behaviour	p. 346
Chiral Networks	p. 352
1D Helices from Achiral Components	p. 352
2D Chiral Nets from Achiral Components	p. 354
3D Chiral Nets from Achiral Components	p. 355
Chiral Ligands	p. 361
Applications	p. 367
References	p. 369
Reactive Coordination Polymers
Introduction	p. 375
Topotactic Reactions	p. 375
Chemically Reactive Ligands	p. 386
Catalysis	p. 386
References	p. 391
Other Properties of Coordination Polymers
Introduction	p. 396
Luminescence	p. 397
Redox Activity	p. 399
Conductivity	p. 401
Negative Thermal Expansion	p. 404
Multifunctional Materials	p. 407
References	p. 408
Subject Index	p. 416
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