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Molecular Magnetic Materials: Concepts and Applications

ISBN: 978-3-527-33953-2
512 pages
January 2017
Molecular Magnetic Materials: Concepts and Applications (3527339531) cover image

Description

A comprehensive overview of this rapidly expanding interdisciplinary field of research.
After a short introduction to the basics of magnetism and molecular magnetism, the text goes on to cover specific properties of molecular magnetic materials as well as their current and future applications. Design strategies for acquiring molecular magnetic materials with desired physical properties are discussed, as are such multifunctional materials as high Tc magnets, chiral and luminescent magnets, magnetic sponges as well as photo- and piezo-switching magnets.
The result is an excellent resource for materials scientists, chemists, physicists and crystal engineers either entering or already working in the field.
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Table of Contents

List of Contributors XV

Preface XXI

1 Magnetism 1
Maria Ba³anda and Robert Pe³ka

1.1 Origin of Magnetism 1

1.2 Macroscopic Approach 3

1.3 Units in Magnetism 5

1.4 Ground State of an Ion and Hund’s Rules 6

1.5 An Atom in a Magnetic Field 9

1.6 Mechanisms of Magnetic Interactions 10

1.7 Collective Magnetic State 17

1.8 Applications and Research 26

References 28

2 Molecular Magnetism 29
Michael Shatruk, Silvia Gómez-Coca, and Kim R. Dunbar

2.1 Introduction 29

2.2 Birth of the Topic: Exchange-Coupled Clusters 29

2.3 Evolution of the Topic: Molecule-Based Magnets 31

2.4 Burgeoning Topics: Single-Molecule Magnets 32

2.5 Single-Chain Magnets 37

2.6 Spin Crossover Complexes 40

2.7 Charge Transfer-Induced Spin Transitions 43

2.8 Multifunctional Materials 44

2.9 Future Perspectives 46

References 48

3 High-Spin Molecules 53
Zhao-Ping Ni andMing-Liang Tong

3.1 Introduction 53

3.2 Strategies for High-Spin Molecules 54

3.3 High-Spin Molecules based on d-Metal Ions 60

3.4 High-Spin Molecules Based on f-Metal Ions 67

3.5 High-Spin Molecules Based on d–f Metal Ions 69

3.6 Conclusions and Perspectives 71

References 72

4 Single Molecule Magnets 79
Masahiro Yamashita and Keiichi Katoh

4.1 Introduction 79

4.2 Measurement Techniques 82

4.3 Rational Design of SMMs 91

4.4 Family of SMMs 93

4.5 Conclusions and Perspectives 97

References 98

5 Magnetic Molecules as Spin Qubits 103
Paolo Santini, Stefano Carretta, and Giuseppe Amoretti

5.1 Introduction 103

5.2 Molecular Qubits 107

5.3 Schemes for Two-Qubit Gates 110

5.4 Conclusions and Perspectives 123

Appendix: The Basics 125

List of Acronyms 127

References 127

6 Single-Chain Magnets 131
Kasper S. Pedersen, Alessandro Vindigni, Roberta Sessoli, Claude Coulon, and Rodolphe Clérac

6.1 Introduction 131

6.2 The Very Basics 132

6.3 Synthetic Endeavors Toward SCMs 135

6.4 Theoretical Modeling 141

6.5 New Directions 150

6.6 Conclusions and Perspectives 155

References 156

7 High-Tc Ordered Molecular Magnets 161
Joel S.Miller and Shin-ichi Ohkoshi

7.1 Introduction 161

7.2 TCNE-BasedMolecule-Based Magnets 163

7.3 Prussian Blue Analogs 168

7.4 Hepta- and Octacyanido-based Molecule-based Magnets 174

7.5 Conclusions and Perspectives 180

References 182

8 Thin Layers of Molecular Magnets 187
Andrea Cornia, Daniel R. Talham, and Marco Affronte

8.1 Introductory Remarks 187

8.2 Thin Layers of Single-Molecule Magnets 188

8.3 Thin Layers of Antiferromagnetic Spin Clusters 206

8.4 Thin Layers of High-Spin Cages 209

8.5 Thin Layers of Molecular Magnets with Extended Networks 211

8.6 Conclusions and Perspectives 218

Acknowledgments 220

References 220

9 Spin Crossover Phenomenon in Coordination Compounds 231
Ana B. Gaspar and Birgit Weber

9.1 Introduction 231

9.2 Spin Crossover in the Solid and Liquid States 232

9.3 Multifunctionality in Spin Crossover Compounds 236

9.4 Spin Crossover Phenomenon in Soft Matter 238

9.5 Spin crossover Phenomenon at the Nanoscale 239

9.6 Charge Transport Properties of Single-Spin Crossover Molecules 245

9.7 Conclusion 245

References 246

10 Porous Molecular Magnets 253
Wei-Xiong Zhang,Ming-Hua Zeng, and Xiao-Ming Chen

10.1 Introduction 253

10.2 PMMs with Spin-State Switching 255

10.3 PMMs with Slow Relaxation of Magnetization 258

10.4 PMMs with Long-Range Magnetic Ordering 264

10.5 PMMs with Switching Between Ferromagnetism and Antiferromagnetism 271

10.6 PMMs with the Magnetism-Modified Through Postsynthetic Process 273

10.7 Conclusions and Perspectives 275

References 276

11 Molecular Magnetic Sponges 279
Dawid Pinkowicz, Robet Podgajny, and Barbara Sieklucka

11.1 Introduction 279

11.2 The First Molecular Magnetic Sponge Systems 281

11.3 CN-Bridged Molecular Magnetic Sponges 283

11.4 Molecular Magnetic Sponges with Bridging Ligands Other Than Cyanide 294

11.5 Conclusions and Perspectives 296

References 297

12 Non-CentrosymmetricMolecular Magnets 301
Cyrille Train, Geert Rikken, and Michel Verdaguer

12.1 Introduction 301

12.2 Synthetic Strategies Toward Non-centrosymmetric Magnets (NCM) 304

12.3 Physicochemical Properties of Non-centrosymmetric Magnets 311

12.4 Conclusion 319

Acknowledgment 319

References 319

13 Molecular Photomagnets 323
Corine Mathonière, Hiroko Tokoro, and Shin-ichi Ohkoshi

13.1 Introduction 323

13.2 Photomagnetic Coordination Networks based on [M(CN)x] (x=6 or 8) 325

13.3 Photomagnetic Polynuclear Molecules Based on [M(CN)x] (x=6 or 8) 333

13.4 Conclusions and Perspectives 340

References 341

14 Luminescent Molecular Magnets 345
Mauro Perfetti, Fabrice Pointillart, Olivier Cador, Lorenzo Sorace, and Lahcène Ouahab

14.1 Introduction 345

14.2 Electronic Structure of Lanthanide Ions 346

14.3 Luminescence of Lanthanide Ions 348

14.4 Magnetism of Lanthanide Ions 351

14.5 Synthetic Strategies to Obtain Luminescent SMMs 352

14.6 Luminescent Lanthanide Single Molecule Magnets 356

14.7 NIR Luminescent-Prolate Lanthanides 360

14.8 Conclusions and Perspectives 365

References 365

15 Conductive Molecular Magnets 369
Yoshihiro Sekine,Wataru Kosaka, Kouji Taniguchi, and HitoshiMiyasaka

15.1 Introduction 369

15.2 Design of Metal Complexes with TTF-Containing Ligands 371

15.3 Hybrid Arrangements of Magnetic Layers and Conducting Stacked Layers 379

15.4 Conductive Magnetic Coordination Frameworks 384

15.5 Purely Organic Systems 391

15.6 Conclusions and Perspectives 397

References 397

16 Molecular Multiferroics 405
Thomas T. M. Palstra and Alexey O. Polyakov

16.1 Multiferroicity 405

16.2 Classification of Multiferroic Materials 406

16.3 Classification of Molecular Multiferroics 407

16.4 Metal–Organic Framework Compounds and Hybrid Perovskites 408

16.5 Charge Order Multiferroics 414

16.6 Conclusions and Perspectives 416

References 416

17 Modeling Magnetic Properties with Density Functional Theory-Based Methods 419
Jordi Cirera and Eliseo Ruiz

17.1 Introduction 419

17.2 Theoretical Analysis of Spin Crossover Systems 423

17.3 DFT Methods to Evaluate Exchange Coupling Constants 424

17.4 DFT Methods to Calculate Magnetic Anisotropy Parameters 431

17.5 DFT Approaches to Calculate Transport Through Magnetic Molecules 435

References 439

18 Ab Initio Modeling and Calculations of Magnetic Properties 447
Jürgen Schnack and Coen de Graaf

18.1 Introduction 447

18.2 Ab Initio Calculations 447

18.3 Spin Hamiltonian Calculations 459

References 469

Index 473

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Author Information

Barbara Sieklucka is currently Full Professor for Inorganic Chemistry at the Jagiellonian University in Krakow, Poland and Head of Inorganic Molecular Materials Group as well as co-founder of the European Institute of Molecular Magnetism. She carries out pioneering research on multifunctional molecular magnets in Poland. Her research activities are focused on the crystal engineering of highly-structured functional molecular materials on the basis of polynuclear cyanido-bridged coordination compounds, which will allow to impose specific functionalities such as dynamics, sorption, magnetism, photomagnetism, porosity, luminescence, chirality, and non-linear optics on the target material, with the ultimate goal of achieving multifunctionality and efficient engineering of the nanospace within the crystal network. This fundamental research has the clear application perspective: it may generate new advanced materials for the construction of nanoscale molecular devices with potential applications in nanotechnology or spintronics such as molecular sensors and switches, magnetic coolers, spin valves and spin logic gates.

Dawid Pinkowicz is currently Associate Professor at the Jagiellonian University in Krakow, Poland. He has received his Ph.D. from Jagiellonian University with Prof. Barbara Sieklucka and then moved to Prof. Masahiro Yamashita for the research project "Photo-Switchable Single-Molecule Quantum Magnets" within the Matsumae International Fellowship Program. Afterwards he has joined Prof. Kim Dunbarīs Group for the research project "Multifunctional Molecular Materials through Cyanide Chemistry" within the Marie Curie International Outgoing Fellowship funded by the European Commission within the 7th Framework Programme. His research interests cover the design of tailor-made functional ligands and complexes for the construction of multifunctional molecular compounds and the electronic and magnetic properties of soft matter under extreme conditions: high pressure and low temperatures.
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