This first introduction to the rapidly growing field of molecular magnetism is written with Masters and Ph D students in mind, while postdocs and other newcomers will also find it an extremely useful guide.
Adopting a clear didactic approach, the authors cover the fundamental concepts, providing many examples and give an overview of the most important techniques and key applications. Although the focus is one lanthanide ions, thus reflecting the current research in the field, the principles and the methods equally apply to other systems.
The result is an excellent textbook from both a scientific and pedagogic point of view.
Innehållsförteckning
Preface XI
1 Introduction 1
1.1 A Nano History of Molecular Magnetism 1
1.2 Molecules, Conductors, and Magnets 4
1.3 Origin of Molecular Magnetism 5
1.4 Playing with the Periodic Table 7
1.5 p Magnetic Orbitals 7
1.6 d Magnetic Orbitals 10
1.7 f Magnetic Orbitals 13
1.8 The Goals of Molecular Magnetism 14
1.9 Why a Book 15
1.10 Outlook 16
1.11 The Applications of Ln 18
1.12 Finally SI versus emu 21
References 22
2 Electronic Structures of Free Ions 25
2.1 The Naked Ions 25
2.2 Spin–Orbit Coupling 28
2.3 Applying a Magnetic Field 31
References 32
3 Electronic Structure of Coordinated Ions 33
3.1 Dressing Ions 33
3.2 The Crystal Field 35
3.3 The aquo Ions 38
3.4 The Angular Overlap Model 40
3.5 The Lantanum(III) with Phthalocyanine (Pc) and Poly Oxo Metalates (POM) 42
3.6 Introducing Magnetic Anisotropy 47
References 49
4 Coordination Chemistry and Molecular Magnetism 51
4.1 Introduction 51
4.2 Pyrazolylborates 52
4.3 Phthalocyanines 53
4.4 Cyclopentadiene and Cyclooctatetraene 54
4.5 Polyoxometalates (POMs) 56
4.6 Diketonates 58
4.7 Nitronyl-nitroxides (NITs) 60
4.8 Carboxylates 62
4.9 Schiff Bases 62
References 65
5 Magnetism of Ions 69
5.1 The Curie Law 69
5.2 The Van Vleck Equation 72
5.3 Anisotropy Steps in 75
References 82
6 Molecular Orbital of Isolated Magnetic Centers 83
6.1 Moving to MO 83
6.2 Correlation Effects 84
6.3 DFT 87
6.4 The Complexity of Simple 88
6.5 DFT and Single Ions 90
6.6 DOTA Complexes, Not Only Contrast 93
References 96
7 Toward the Molecular Ferromagnet 99
7.1 Introduction 99
7.2 A Road to Infinite 102
7.3 Magnetic Interactions 104
7.4 Introducing Interactions: Dipolar 110
7.5 Spin Hamiltonians 113
7.6 The Giant Spin 114
7.7 Single Building Block 115
7.8 Multicenter Interactions 115
7.9 Noncollinearity 117
7.10 Introducing Orbital Degeneracy 119
References 124
8 Molecular Orbital of Coupled Systems 127
8.1 Exchange and Superexchange 127
8.2 Structure and Magnetic Correlations: d Orbitals 129
8.3 Quantum Chemical Calculations of SH Parameters 130
8.4 Copper Acetate! 132
8.5 Mixed Pairs: Degenerate–Nondegenerate 136
8.6 f Orbitals and Orbital Degeneracy 138
References 140
9 Structure and Properties of p Magnetic Orbitals Systems 143
9.1 Magnetic Coupling in Organics 143
9.2 Magnetism in Nitroxides 145
9.3 Thioradicals 147
9.4 Metallorganic Magnets 149
9.5 Semiquinone Radicals 152
9.6 NITR Radicals with Metals 155
9.7 Long Distance Interactions in Nitroxides 158
References 160
10 Structure and Properties of Coupled Systems: d, f 163
10.1 d Orbitals 163
10.2 3d 164
10.3 4d and 5d 165
10.4 Introducing Chirality 169
10.5 f-d Interactions 171
10.6 A Model DFT Calculation 172
10.7 Magneto-Structural Correlations in Gd-Cu 173
10.8 f Orbital Systems and Orbital Degeneracy 176
References 177
11 Dynamic Properties 179
11.1 Introductory Remarks 179
11.2 Spin–Lattice Relaxation and T1 181
11.3 Phonons and Direct Mechanism 182
11.4 Two Is Better than One 185
11.5 Playing with Fields 187
11.6 Something Real 189
11.7 Spin–Spin Relaxation and T2 191
References 193
12 SMM Past and Present 195
12.1 Mn12, the Start 195
12.2 Some Basic Magnetism 198
12.3 Fe4 Structure and Magnetic Properties 201
12.4 Fe4 Relaxation and Quantum Tunneling 205
12.5 And τ0? 207
12.6 Deep in the Tunnel 207
12.7 Magnetic Dilution Effects 210
12.8 Single Molecule Magnetism 211
References 213
13 Single Ion Magnet (SIM) 217
13.1 Why Single 217
13.2 Slow Relaxation in Ho in Inorganic Lattice 218
13.3 Quantum Tunneling of the Magnetization: the Role of Nuclei 219
13.4 Back to Magnets 222
13.5 The Phthalocyanine Family: Some More Chemistry 223
13.6 The Anionic Double Decker 224
13.7 CF Aspects 225
13.8 The Breakthrough 226
13.9 Multiple Deckers 229
13.10 The Polyoxometalate Family 231
13.11 More SIM 233
13.12 Perspectives 235
References 236
14 SMM with Lanthanides 239
14.1 SMM with Lanthanides 239
14.2 More Details on SMM with Lanthanides 245
14.3 New Opportunities 247
References 249
15 Single Chain Magnets (SCM) and More 251
15.1 Why 1D 251
15.2 The Glauber Model 253
15.3 SCM: the d and p Way 257
15.4 Spin Glass 259
15.5 Noncollinear One-dimensional Systems 260
15.6 f Orbitals in Chains: Gd 262
15.7 f Orbitals in Chains: Dy 266
15.8 Back to Family 271
References 274
16 Magic Dysprosium 277
16.1 Exploring Single Crystals 277
16.2 The Role of Excited States 282
16.3 A Comparative Look 289
16.4 Dy as a Perturbation 292
References 293
17 Molecular Spintronics 295
17.1 What? 295
17.2 Molecules and Mobile Electrons 297
17.3 Of Molecules and Surfaces 302
17.4 Choosing Molecules and Surfaces 305
17.5 Is it Clean? 307
17.6 X-Rays for Magnetism 308
17.7 Measuring Magnetism on Surfaces 310
17.8 Transport through Single Radicals 311
17.9 Pc Family 314
17.10 Mn12 Forever 317
17.11 Hybrid Organic and f Orbitals 318
17.12 Magnetically Active Substrates 319
17.13 Using Nuclei 321
17.14 Some Device at Last 324
References 325
18 Hunting for Quantum Effects 329
18.1 From Classic to Quantum 329
18.2 Basic QIP 331
18.3 A Detour 334
18.4 Endohedral Fullerenes 335
18.5 Criteria for QIP 338
18.6 Starting from Inorganic 340
18.7 Molecular Rings 341
18.8 V15 346
18.9 Qubit Manipulation 347
18.10 Some Philosophy 347
References 348
19 Controlling the Growth 351
19.1 Introduction 351
19.2 Metal–Organic Frameworks MOFs 352
19.3 From Nano to Giant 358
19.4 Molybdates 358
19.5 To the Limit 360
19.6 Controlling Anisotropy 363
19.7 Cluster with Few Lanthanides 365
19.8 Analyzing the Magnetic Properties 366
19.9 Two-Dimensional Structures 369
References 371
20 ESR 375
20.1 A Bird’s Eye View of ESR of Ln 375
20.2 Gd in Detail 376
20.3 Gd with Radicals 379
20.4 Including Orbit 381
20.5 Involving TM 384
20.6 Ln Nicotinates 388
20.7 Measuring Distances 391
References 392
21 NMR 395
21.1 NMR of Rare Earth Nuclides 395
21.2 NMR of Lanthanide Ions in Solution 395
21.3 Lanthanide Shift Reagents (LSR) 404
References 407
22 Magnetic Resonance Imaging 409
22.1 Chemical Exchange Saturation Transfer (CEST) 415
References 419
23 Some Applications of MM 421
23.1 Magnetocaloric Effect 421
23.2 Luminescence 424
23.2.1 Electroluminescent Materials for OLED 429
23.2.2 Biological Assays and Medical Imaging 432
References 432
Appendix A 435
Appendix B 437
Index 439
Om författaren
Dante Gatteschi is Professor of General and Inorganic Chemistry at the University of Florence since 1980. Before his professorship, he studied at the University of Florence and then obtained a position of Assistente with Professor Luigi Sacconi. His current research interests focus on molecular magnetism, including the design and synthesis of molecular magnetic materials as well as single-molecule magnets. He is on several editorial boards and has received many international awards. Currently he has over 600 publications.
Cristiano Benelli is Professor of Chemistry at the University of Florence. He has spent his whole academic career at the University of Florence, first as a student, then as Assistente with Professor Luigi Sacconi and Professor Ivano Bertini, before becoming Professor. His research interests include magnetic materials, low-dimensional systems as well as investigating spectrosopic and theoretical properties of transiton metal complexes.
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