Chapter 1 Introduction
1.1 Introduction ............................................... 1
1.2 Crystal Engineering, Supramolecular Chemistry,
Metallosupramolecules ...................................... 4
1.3 What is a Coordination Polymer? ............................ 6
1.4 Synthetic Techniques ...................................... 10
1.5 Design, Analysis, Application ............................. 12
References ................................................ 13
Chapter 2 Nets: A Tool for Description and Design
2.1 Introduction .............................................. 19
2.2 Defining Networks ......................................... 20
2.3 Identifying and Naming Nets ............................... 25
2.4 ID Nets ................................................... 28
2.5 2D Nets ................................................... 29
2.6 Common 3D Nets ............................................ 36
2.7 Rod Packings .............................................. 52
References ................................................ 53
Chapter 3 Interpenetration
3.1 Introduction .............................................. 59
3.2 Nomenclature .............................................. 67
3.3 ID Interpenetration ....................................... 69
3.4 2D Interpenetration ....................................... 70
3.5 3D Interpenetration ....................................... 77
3.6 Interpenetration of Nets of Different Composition,
Topology and Dimensions ................................... 84
3.7 Self-penetration .......................................... 87
3.8 Other Entangled Systems ................................... 89
References ................................................ 89
Chapter 4 Malleability of Coordination Polymers
4.1 Introduction .............................................. 96
4.2 Supramolecular Isomerism .................................. 98
4.3 Malleability of Building Blocks .......................... 107
4.4 Synthetic Approach ....................................... 111
4.5 Solvent Effects .......................................... 115
4.6 Other Guests ............................................. 119
4.7 Counterions .............................................. 120
4.8 Weaker Interactions ...................................... 124
4.9 Conclusion ............................................... 134
References ............................................... 134
Chapter 5 Transition Metal Coordination Polymers
5.1 Introduction ............................................. 144
5.2 Pseudohalide Ligands ..................................... 146
5.3 Larger Nitrile Donor Ligands ............................. 156
5.4 Pyridyl Donor Ligands .................................... 159
5.5 Five-membered Ring Nitrogen Donor Ligands ................ 166
5.6 N-Oxide Ligands .......................................... 170
5.7 Carboxylate Ligands ...................................... 172
5.8 Other Ligands ............................................ 178
5.9 Mixed Donor Atom Ligands ................................. 180
5.10 Mixed Ligand Coordination Polymers ....................... 181
References .................................................... 183
Chapter 6 Rare Earth Coordination Polymers
6.1 Introduction ............................................. 191
6.2 Cyanide/Nitrile and Pseudohalide Ligands ................. 192
6.3 Five-membered Ring Donors ................................ 195
6.4 Pyridyl Donor Ligands .................................... 196
6.5 N-Oxide Donors ........................................... 196
6.6 Rare Earth-Carboxylate Polymers .......................... 202
6.7 Other Ligands ............................................ 212
6.8 Mixed 3d/4f Coordination Polymers ........................ 221
6.9 Actinide Coordination Polymers ........................... 229
References .................................................... 231
Chapter 7 Organometallic Networks
7.1 Introduction ............................................. 238
7.2 Large Aromatic Ligands ................................... 239
7.3 Organometallic Complexes as Ligands ...................... 245
7.4 Isocarbonyl Polymers ..................................... 248
7.5 R3Sn/R3Pb Systems ........................................ 251
References .................................................... 254
Chapter 8 Inorganic-Organic Hybrids
8.1 Introduction ............................................. 257
8.2 OD Metal-Oxide Substructures ............................. 259
8.3 ID Metal-Oxide Substructures ............................. 260
8.4 2D Metal-Oxide Substructures (Pillared Layers) ........... 264
References .................................................... 271
Chapter 9 Magnetism in Coordination Polymers
9.1 Introduction ............................................. 273
9.2 Long-range Magnetic Ordering ............................. 273
9.3 Spin Crossover ........................................... 295
References .................................................... 307
Chapter 10 Porous Coordination Polymers
10.1 Introduction ............................................. 313
10.2 Designing Permanent Porosity ............................. 315
10.3 Solvent Exchange ......................................... 326
10.4 Gas Storage .............................................. 330
10.5 Ion Exchange ............................................. 338
10.6 Multifunctional Porous Materials ......................... 338
10.7 Conclusion ............................................... 340
References .................................................... 341
Chapter 11 Acentric and Chiral Networks
11.1 Introduction ............................................. 345
11.2 Acentric Networks for Non-linear Optical Behaviour ....... 346
11.3 Chiral Networks .......................................... 352
References .................................................... 369
Chapter 12 Reactive Coordination Polymers
12.1 Introduction ............................................. 375
12.2 Topotactic Reactions ..................................... 375
12.3 Chemically Reactive Ligands .............................. 386
12.4 Catalysis ................................................ 386
References .................................................... 391
Chapter 13 Other Properties of Coordination Polymers .......... 416
13.1 Introduction ............................................. 396
13.2 Luminescence ............................................. 397
13.3 Redox Activity ........................................... 399
13.4 Conductivity ............................................. 401
13.5 Negative Thermal Expansion ............................... 404
13.6 Multifunctional Materials ................................ 407
References .................................................... 408
Subject Index ................................................. 416
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