Details

Introduction to Molecular Magnetism

From Transition Metals to Lanthanides
1. Aufl.

von: Cristiano Benelli, Dante Gatteschi
102,99 €
Verlag:	Wiley-VCH
Format:	PDF
Veröffentl.:	16.04.2015
ISBN/EAN:	9783527690565
Sprache:	englisch
Anzahl Seiten:	520

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Beschreibungen

Titelbeschreibung

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.

Inhaltsverzeichnis

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

Autorenportrait

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.

Back cover copy

Magnets are versatile and found in many everyday items; even molecules themselves can act as tiny magnets. This book is an introduction to the rapidly growing field of molecular magnetism 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 giving an overview of the most important techniques and key applications. Although the focus is on lanthanide ions, thus reflecting the current research in the field, the principles and the methods can easily be applied to other systems. The result is an excellent textbook from both a scientific and pedagogic point of view.