The fundamentals of molecular magnetism (216,00 руб.)

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UDC 542.8+537(078) L 84 L 84 Lukov, V. V., Shcherbakov I. N. Fundamentals of molecular magnetism : textbook / ISBN 978-5-9275-2691-8 Molecular magnetism occupies a crossing point between two V. V. Lukov, I. N. Shcherbakov ; Southern Federal University. – Rostov-on-Don ; Taganrog : Publishing House of Southern Federal University, 2017. – 180 p. fields of research-materials science and metal biochemistry – and plays an important role in the field of molecular electronics. The “Fundamentals of molecular magnetism” is the textbook to comprehensively address both the experimental and theoretical aspects of the relatively new field of research. It introduces the basic concepts concerning magnetization and magnetic susceptibility, establishes the fundamental equations of molecular magnetism and examines molecules containing a unique magnetic center, including the highspin- low- spin transition compounds. The textbook highlights polymetallic species, reviews the phenomenon of interaction between spin carriers from a theoretical point of view and includes numerous examples throughout to illustrate the topics discussed. An essential part of the textbook is devoted to novel class of magneto active materials- single molecular magnets (SMMs) ISBN 978-5-9275-2691-8 UDC 542.8+537(078) © Southern Federal University, 2017 © Lukov V. V., Shcherbakov I. N., 2017

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CONTENTS I. Introduction ........................................................................... 4 II. History of Magnetic measurements ................................ 6 III. Basic concepts .................................................................... 7 III. 1. Magnetisation and Susceptibility ................................ 7 III. 2. Diamagnetism .............................................................. 9 III. 3. Paramagnetism. The Curie and Curie–Weiss Laws ........................................................................................... 12 IV. Orbital Angular Momentum .......................................... 18 IV. 1. Ligand Field Quenching of Orbital Angular Momentum ................................................................................ 19 IV. 2. Explanation of Ligand Field Quenching ................... 20 IV. 3. Spin-Orbit Coupling ................................................... 22 IV. 4. Rare Earth Ions .......................................................... 24 V. The Van Vleck equation ................................................... 26 V. 1. Application of the Van Vleck Formula to an Isolated, Spin-Only Metal Complex .......................................... 27 V. 2. Deviations from the Curie Law: Zero-Field Splitting ...................................................................................... 28 VI. Electron Paramagnetic Resonance (EPR) ................. 30 VII. Low-Spin-High-Spin Transition .................................. 35 VII. 1. High-Spin Molar Fraction versus Temperature Curves for Spin Transition Compounds .................................. 37 VII. 2. Mechanism of the Spin Transition at the Molecular Scale .......................................................................... 38 VII. 3. Spin Transition and Cooperativity ........................... 43 VII. 4. Regular Solution Model ............................................ 45 VII. 5. Domain Model ........................................................... 53 VII. 6. Some Selected Examples .......................................... 56 VII. 6. 1. d4 VII. 6. 2. d5 VII. 6. 3. d6 VII. 6. 4. d7 Ions ................................................................. 56 Ions ................................................................. 58 Ions ................................................................ 61 Ions ................................................................ 69 VII. 7. Spin Transition and Molecular Electronics ............. 71 VIII. Isotropic Interaction in Dinuclear Compounds .... 74 VIII. 1. Copper(ll) Dinuclear Compounds ............................ 74 VIII. 2. Other Symmetrical Dinuclear Compounds ............ 85 3

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VIII. 3. Asymmetrical Dinuclear Compounds ..................... 94 VIII. 4. Influence of the Local Anisotropy ......................... 101 VIII. 5. Intermolecular Interactions between Dinuclear Units ........................................................................ 108 IX. Single Molecule Magnets .............................................. 110 IX. 1. Introduction .............................................................. 110 IX. 2. A Brief Introduction to the Physics of SMMs .......... 111 IX. 3. Further SMMs Based on Mn(III) ............................. 115 IX. 3. 1. The largest SMM; a [Mn84 relaxation ................................................................................. 116 IX. 3. 3. Record magnetic anisotropy barrier; a Mn6 IX. 3. 2. Record spin number, ST = 83/2, but no slow cluster ....................................................................................... 117 IX. 3. 4. Quantum entanglement between SMMs; first discovered in a pair of Mn4 clusters ............................... 117 IX. 3. 5. [MnIII state .......................................................................................... 118 IX. 3. 6. The [MnIII 3 MnIV ] clusters with an S = 9/2 ground and ST IX. 3. 7. Oxime bridged SMMs with the core [MnIII 2 MnII a family of [MnIII 2] family of “rhombic” SMMs .. 121 3O] = 6 .................................................................................. 125 IX. 3. 8. Magnetostructural correlations within 6] SMMs ........................................................ 128 IX. 4. MMs Based on Fe(III) Ions....................................... 131 IX. 5. New SMMs Based on Divalent 3d-Ions ................... 132 IX. 6. Slow Relaxation in Complexes Involving 4f-Elements .............................................................................. 139 IX. 6. 1. Single atom magnets ........................................ 139 IX. 6. 2. Polymetallic 4f-complexes ................................ 140 IX. 6. 3. Heterometallic 3d-4f SMMs ............................. 142 IX. 7. Metallocyanate Based SMMs ................................... 147 IX. 8. Conclusions ............................................................... 148 X. Exercises ............................................................................ 149 References .............................................................................. 155 ] torus ..................... 115 4

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