Introduction to Molecular Magnetism From

This first introduction to the rapidly growing field of molecular magnetism is written with Masters and PhD 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.

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.

Preface XI

1 Introduction 1

1.1 A Nano History of Molecular Magnetism 1

1.2 Molecules, Conductors, and Magnets 4

1.3 Origin ofMolecular 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 PolyOxoMetalates (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 pWay 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

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Introduction to Molecular Magnetism From Transition Metals to Lanthanides

Summary

Author Biography

Table of Contents

Supplemental Materials