Introduction to Molecular Magnetism

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.

Autorentext
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.

Klappentext

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.

Inhalt

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 SpinOrbit 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: DegenerateNondegenerate 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 SpinLattice 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</p...