Molecular Magnetic Materials

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 Dunbar's 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.

• List of Contributors XVPreface XXI1 Magnetism 1Maria Ba³anda and Robert Pe³ka1.1 Origin of Magnetism 11.2 Macroscopic Approach 31.3 Units in Magnetism 51.4 Ground State of an Ion and Hund’s Rules 61.5 An Atom in a Magnetic Field 91.6 Mechanisms of Magnetic Interactions 101.7 Collective Magnetic State 171.8 Applications and Research 26References 282 Molecular Magnetism 29Michael Shatruk, Silvia Gómez-Coca, and Kim R. Dunbar2.1 Introduction 292.2 Birth of the Topic: Exchange-Coupled Clusters 292.3 Evolution of the Topic: Molecule-Based Magnets 312.4 Burgeoning Topics: Single-Molecule Magnets 322.5 Single-Chain Magnets 372.6 Spin Crossover Complexes 402.7 Charge Transfer-Induced Spin Transitions 432.8 Multifunctional Materials 442.9 Future Perspectives 46References 483 High-Spin Molecules 53Zhao-Ping Ni andMing-Liang Tong3.1 Introduction 533.2 Strategies for High-Spin Molecules 543.3 High-Spin Molecules based on d-Metal Ions 603.4 High-Spin Molecules Based on f-Metal Ions 673.5 High-Spin Molecules Based on d–f Metal Ions 693.6 Conclusions and Perspectives 71References 724 Single Molecule Magnets 79Masahiro Yamashita and Keiichi Katoh4.1 Introduction 794.2 Measurement Techniques 824.3 Rational Design of SMMs 914.4 Family of SMMs 934.5 Conclusions and Perspectives 97References 985 Magnetic Molecules as Spin Qubits 103Paolo Santini, Stefano Carretta, and Giuseppe Amoretti5.1 Introduction 1035.2 Molecular Qubits 1075.3 Schemes for Two-Qubit Gates 1105.4 Conclusions and Perspectives 123Appendix: The Basics 125List of Acronyms 127References 1276 Single-Chain Magnets 131Kasper S. Pedersen, Alessandro Vindigni, Roberta Sessoli, Claude Coulon, and Rodolphe Clérac6.1 Introduction 1316.2 The Very Basics 1326.3 Synthetic Endeavors Toward SCMs 1356.4 Theoretical Modeling 1416.5 New Directions 1506.6 Conclusions and Perspectives 155References 1567 High-Tc Ordered Molecular Magnets 161Joel S.Miller and Shin-ichi Ohkoshi7.1 Introduction 1617.2 TCNE-BasedMolecule-Based Magnets 1637.3 Prussian Blue Analogs 1687.4 Hepta- and Octacyanido-based Molecule-based Magnets 1747.5 Conclusions and Perspectives 180References 1828 Thin Layers of Molecular Magnets 187Andrea Cornia, Daniel R. Talham, and Marco Affronte8.1 Introductory Remarks 1878.2 Thin Layers of Single-Molecule Magnets 1888.3 Thin Layers of Antiferromagnetic Spin Clusters 2068.4 Thin Layers of High-Spin Cages 2098.5 Thin Layers of Molecular Magnets with Extended Networks 2118.6 Conclusions and Perspectives 218Acknowledgments 220References 2209 Spin Crossover Phenomenon in Coordination Compounds 231Ana B. Gaspar and Birgit Weber9.1 Introduction 2319.2 Spin Crossover in the Solid and Liquid States 2329.3 Multifunctionality in Spin Crossover Compounds 2369.4 Spin Crossover Phenomenon in Soft Matter 2389.5 Spin crossover Phenomenon at the Nanoscale 2399.6 Charge Transport Properties of Single-Spin Crossover Molecules 2459.7 Conclusion 245References 24610 Porous Molecular Magnets 253Wei-Xiong Zhang,Ming-Hua Zeng, and Xiao-Ming Chen10.1 Introduction 25310.2 PMMs with Spin-State Switching 25510.3 PMMs with Slow Relaxation of Magnetization 25810.4 PMMs with Long-Range Magnetic Ordering 26410.5 PMMs with Switching Between Ferromagnetism and Antiferromagnetism 27110.6 PMMs with the Magnetism-Modified Through Postsynthetic Process 27310.7 Conclusions and Perspectives 275References 27611 Molecular Magnetic Sponges 279Dawid Pinkowicz, Robet Podgajny, and Barbara Sieklucka11.1 Introduction 27911.2 The First Molecular Magnetic Sponge Systems 28111.3 CN-Bridged Molecular Magnetic Sponges 28311.4 Molecular Magnetic Sponges with Bridging Ligands Other Than Cyanide 29411.5 Conclusions and Perspectives 296References 29712 Non-CentrosymmetricMolecular Magnets 301Cyrille Train, Geert Rikken, and Michel Verdaguer12.1 Introduction 30112.2 Synthetic Strategies Toward Non-centrosymmetric Magnets (NCM) 30412.3 Physicochemical Properties of Non-centrosymmetric Magnets 31112.4 Conclusion 319Acknowledgment 319References 31913 Molecular Photomagnets 323Corine Mathonière, Hiroko Tokoro, and Shin-ichi Ohkoshi13.1 Introduction 32313.2 Photomagnetic Coordination Networks based on [M(CN)x] (x=6 or 8) 32513.3 Photomagnetic Polynuclear Molecules Based on [M(CN)x] (x=6 or 8) 33313.4 Conclusions and Perspectives 340References 34114 Luminescent Molecular Magnets 345Mauro Perfetti, Fabrice Pointillart, Olivier Cador, Lorenzo Sorace, and Lahcène Ouahab14.1 Introduction 34514.2 Electronic Structure of Lanthanide Ions 34614.3 Luminescence of Lanthanide Ions 34814.4 Magnetism of Lanthanide Ions 35114.5 Synthetic Strategies to Obtain Luminescent SMMs 35214.6 Luminescent Lanthanide Single Molecule Magnets 35614.7 NIR Luminescent-Prolate Lanthanides 36014.8 Conclusions and Perspectives 365References 36515 Conductive Molecular Magnets 369Yoshihiro Sekine,Wataru Kosaka, Kouji Taniguchi, and HitoshiMiyasaka15.1 Introduction 36915.2 Design of Metal Complexes with TTF-Containing Ligands 37115.3 Hybrid Arrangements of Magnetic Layers and Conducting Stacked Layers 37915.4 Conductive Magnetic Coordination Frameworks 38415.5 Purely Organic Systems 39115.6 Conclusions and Perspectives 397References 39716 Molecular Multiferroics 405Thomas T. M. Palstra and Alexey O. Polyakov16.1 Multiferroicity 40516.2 Classification of Multiferroic Materials 40616.3 Classification of Molecular Multiferroics 40716.4 Metal–Organic Framework Compounds and Hybrid Perovskites 40816.5 Charge Order Multiferroics 41416.6 Conclusions and Perspectives 416References 41617 Modeling Magnetic Properties with Density Functional Theory-Based Methods 419Jordi Cirera and Eliseo Ruiz17.1 Introduction 41917.2 Theoretical Analysis of Spin Crossover Systems 42317.3 DFT Methods to Evaluate Exchange Coupling Constants 42417.4 DFT Methods to Calculate Magnetic Anisotropy Parameters 43117.5 DFT Approaches to Calculate Transport Through Magnetic Molecules 435References 43918 Ab Initio Modeling and Calculations of Magnetic Properties 447Jürgen Schnack and Coen de Graaf18.1 Introduction 44718.2 Ab Initio Calculations 44718.3 Spin Hamiltonian Calculations 459References 469Index 473