Introduction to Molecular Magnetism

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 XI1 Introduction 11.1 A Nano History of Molecular Magnetism 11.2 Molecules, Conductors, and Magnets 41.3 Origin ofMolecular Magnetism 51.4 Playing with the Periodic Table 71.5 p Magnetic Orbitals 71.6 d Magnetic Orbitals 101.7 f Magnetic Orbitals 131.8 The Goals of Molecular Magnetism 141.9 Why a Book 151.10 Outlook 161.11 The Applications of Ln 181.12 Finally SI versus emu 21References 222 Electronic Structures of Free Ions 252.1 The Naked Ions 252.2 Spin–Orbit Coupling 282.3 Applying a Magnetic Field 31References 323 Electronic Structure of Coordinated Ions 333.1 Dressing Ions 333.2 The Crystal Field 353.3 The aquo Ions 383.4 The Angular Overlap Model 403.5 The Lantanum(III) with Phthalocyanine (Pc) and PolyOxoMetalates (POM) 423.6 Introducing Magnetic Anisotropy 47References 494 Coordination Chemistry and Molecular Magnetism 514.1 Introduction 514.2 Pyrazolylborates 524.3 Phthalocyanines 534.4 Cyclopentadiene and Cyclooctatetraene 544.5 Polyoxometalates (POMs) 564.6 Diketonates 584.7 Nitronyl-nitroxides (NITs) 604.8 Carboxylates 624.9 Schiff Bases 62References 655 Magnetism of Ions 695.1 The Curie Law 695.2 The Van Vleck Equation 725.3 Anisotropy Steps in 75References 826 Molecular Orbital of Isolated Magnetic Centers 836.1 Moving to MO 836.2 Correlation Effects 846.3 DFT 876.4 The Complexity of Simple 886.5 DFT and Single Ions 906.6 DOTA Complexes, Not Only Contrast 93References 967 Toward the Molecular Ferromagnet 997.1 Introduction 997.2 A Road to Infinite 1027.3 Magnetic Interactions 1047.4 Introducing Interactions: Dipolar 1107.5 Spin Hamiltonians 1137.6 The Giant Spin 1147.7 Single Building Block 1157.8 Multicenter Interactions 1157.9 Noncollinearity 1177.10 Introducing Orbital Degeneracy 119References 1248 Molecular Orbital of Coupled Systems 1278.1 Exchange and Superexchange 1278.2 Structure and Magnetic Correlations: d Orbitals 1298.3 Quantum Chemical Calculations of SH Parameters 1308.4 Copper Acetate! 1328.5 Mixed Pairs: Degenerate–Nondegenerate 1368.6 f Orbitals and Orbital Degeneracy 138References 1409 Structure and Properties of p Magnetic Orbitals Systems 1439.1 Magnetic Coupling in Organics 1439.2 Magnetism in Nitroxides 1459.3 Thioradicals 1479.4 Metallorganic Magnets 1499.5 Semiquinone Radicals 1529.6 NITR Radicals with Metals 1559.7 Long Distance Interactions in Nitroxides 158References 16010 Structure and Properties of Coupled Systems: d, f 16310.1 d Orbitals 16310.2 3d 16410.3 4d and 5d 16510.4 Introducing Chirality 16910.5 f-d Interactions 17110.6 A Model DFT Calculation 17210.7 Magneto-Structural Correlations in Gd-Cu 17310.8 f Orbital Systems and Orbital Degeneracy 176References 17711 Dynamic Properties 17911.1 Introductory Remarks 17911.2 Spin–Lattice Relaxation and T1 18111.3 Phonons and Direct Mechanism 18211.4 Two Is Better than One 18511.5 Playing with Fields 18711.6 Something Real 18911.7 Spin–Spin Relaxation and T2 191References 19312 SMM Past and Present 19512.1 Mn12, the Start 19512.2 Some Basic Magnetism 19812.3 Fe4 Structure and Magnetic Properties 20112.4 Fe4 Relaxation and Quantum Tunneling 20512.5 And τ0? 20712.6 Deep in the Tunnel 20712.7 Magnetic Dilution Effects 21012.8 Single Molecule Magnetism 211References 21313 Single Ion Magnet (SIM) 21713.1 Why Single 21713.2 Slow Relaxation in Ho in Inorganic Lattice 21813.3 Quantum Tunneling of the Magnetization: the Role of Nuclei 21913.4 Back to Magnets 22213.5 The Phthalocyanine Family: Some More Chemistry 22313.6 The Anionic Double Decker 22413.7 CF Aspects 22513.8 The Breakthrough 22613.9 Multiple Deckers 22913.10 The Polyoxometalate Family 23113.11 More SIM 23313.12 Perspectives 235References 23614 SMM with Lanthanides 23914.1 SMM with Lanthanides 23914.2 More Details on SMM with Lanthanides 24514.3 New Opportunities 247References 24915 Single Chain Magnets (SCM) and More 25115.1 Why 1D 25115.2 The Glauber Model 25315.3 SCM: the d and pWay 25715.4 Spin Glass 25915.5 Noncollinear One-dimensional Systems 26015.6 f Orbitals in Chains: Gd 26215.7 f Orbitals in Chains: Dy 26615.8 Back to Family 271References 27416 Magic Dysprosium 27716.1 Exploring Single Crystals 27716.2 The Role of Excited States 28216.3 A Comparative Look 28916.4 Dy as a Perturbation 292References 29317 Molecular Spintronics 29517.1 What? 29517.2 Molecules and Mobile Electrons 29717.3 Of Molecules and Surfaces 30217.4 Choosing Molecules and Surfaces 30517.5 Is it Clean? 30717.6 X-Rays for Magnetism 30817.7 Measuring Magnetism on Surfaces 31017.8 Transport through Single Radicals 31117.9 Pc Family 31417.10 Mn12 Forever 31717.11 Hybrid Organic and f Orbitals 31817.12 Magnetically Active Substrates 31917.13 Using Nuclei 32117.14 Some Device at Last 324References 32518 Hunting for Quantum Effects 32918.1 From Classic to Quantum 32918.2 Basic QIP 33118.3 A Detour 33418.4 Endohedral Fullerenes 33518.5 Criteria for QIP 33818.6 Starting from Inorganic 34018.7 Molecular Rings 34118.8 V15 34618.9 Qubit Manipulation 34718.10 Some Philosophy 347References 34819 Controlling the Growth 35119.1 Introduction 35119.2 Metal–Organic Frameworks MOFs 35219.3 From Nano to Giant 35819.4 Molybdates 35819.5 To the Limit 36019.6 Controlling Anisotropy 36319.7 Cluster with Few Lanthanides 36519.8 Analyzing the Magnetic Properties 36619.9 Two-Dimensional Structures 369References 37120 ESR 37520.1 A Bird’s Eye View of ESR of Ln 37520.2 Gd in Detail 37620.3 Gd with Radicals 37920.4 Including Orbit 38120.5 Involving TM 38420.6 Ln Nicotinates 38820.7 Measuring Distances 391References 39221 NMR 39521.1 NMR of Rare Earth Nuclides 39521.2 NMR of Lanthanide Ions in Solution 39521.3 Lanthanide Shift Reagents (LSR) 404References 40722 Magnetic Resonance Imaging 40922.1 Chemical Exchange Saturation Transfer (CEST) 415References 41923 Some Applications of MM 42123.1 Magnetocaloric Effect 42123.2 Luminescence 42423.2.1 Electroluminescent Materials for OLED 42923.2.2 Biological Assays and Medical Imaging 432References 432Appendix A 435Appendix B 437Index 439