Details

Introduction to Molecular Magnetism


Introduction to Molecular Magnetism

From Transition Metals to Lanthanides
1. Aufl.

von: Cristiano Benelli, Dante Gatteschi

93,99 €

Verlag: Wiley-VCH
Format: PDF
Veröffentl.: 16.04.2015
ISBN/EAN: 9783527690565
Sprache: englisch
Anzahl Seiten: 520

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Beschreibungen

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. <br> 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.<br> The result is an excellent textbook from both a scientific and pedagogic point of view.
<p>Preface XI</p> <p><b>1 Introduction 1</b></p> <p>1.1 A Nano History of Molecular Magnetism 1</p> <p>1.2 Molecules, Conductors, and Magnets 4</p> <p>1.3 Origin ofMolecular Magnetism 5</p> <p>1.4 Playing with the Periodic Table 7</p> <p>1.5 p Magnetic Orbitals 7</p> <p>1.6 d Magnetic Orbitals 10</p> <p>1.7 f Magnetic Orbitals 13</p> <p>1.8 The Goals of Molecular Magnetism 14</p> <p>1.9 Why a Book 15</p> <p>1.10 Outlook 16</p> <p>1.11 The Applications of Ln 18</p> <p>1.12 Finally SI versus emu 21</p> <p>References 22</p> <p><b>2 Electronic Structures of Free Ions 25</b></p> <p>2.1 The Naked Ions 25</p> <p>2.2 Spin–Orbit Coupling 28</p> <p>2.3 Applying a Magnetic Field 31</p> <p>References 32</p> <p><b>3 Electronic Structure of Coordinated Ions 33</b></p> <p>3.1 Dressing Ions 33</p> <p>3.2 The Crystal Field 35</p> <p>3.3 The aquo Ions 38</p> <p>3.4 The Angular Overlap Model 40</p> <p>3.5 The Lantanum(III) with Phthalocyanine (Pc) and PolyOxoMetalates (POM) 42</p> <p>3.6 Introducing Magnetic Anisotropy 47</p> <p>References 49</p> <p><b>4 Coordination Chemistry and Molecular Magnetism 51</b></p> <p>4.1 Introduction 51</p> <p>4.2 Pyrazolylborates 52</p> <p>4.3 Phthalocyanines 53</p> <p>4.4 Cyclopentadiene and Cyclooctatetraene 54</p> <p>4.5 Polyoxometalates (POMs) 56</p> <p>4.6 Diketonates 58</p> <p>4.7 Nitronyl-nitroxides (NITs) 60</p> <p>4.8 Carboxylates 62</p> <p>4.9 Schiff Bases 62</p> <p>References 65</p> <p><b>5 Magnetism of Ions 69</b></p> <p>5.1 The Curie Law 69</p> <p>5.2 The Van Vleck Equation 72</p> <p>5.3 Anisotropy Steps in 75</p> <p>References 82</p> <p><b>6 Molecular Orbital of Isolated Magnetic Centers 83</b></p> <p>6.1 Moving to MO 83</p> <p>6.2 Correlation Effects 84</p> <p>6.3 DFT 87</p> <p>6.4 The Complexity of Simple 88</p> <p>6.5 DFT and Single Ions 90</p> <p>6.6 DOTA Complexes, Not Only Contrast 93</p> <p>References 96</p> <p><b>7 Toward the Molecular Ferromagnet 99</b></p> <p>7.1 Introduction 99</p> <p>7.2 A Road to Infinite 102</p> <p>7.3 Magnetic Interactions 104</p> <p>7.4 Introducing Interactions: Dipolar 110</p> <p>7.5 Spin Hamiltonians 113</p> <p>7.6 The Giant Spin 114</p> <p>7.7 Single Building Block 115</p> <p>7.8 Multicenter Interactions 115</p> <p>7.9 Noncollinearity 117</p> <p>7.10 Introducing Orbital Degeneracy 119</p> <p>References 124</p> <p><b>8 Molecular Orbital of Coupled Systems 127</b></p> <p>8.1 Exchange and Superexchange 127</p> <p>8.2 Structure and Magnetic Correlations: d Orbitals 129</p> <p>8.3 Quantum Chemical Calculations of SH Parameters 130</p> <p>8.4 Copper Acetate! 132</p> <p>8.5 Mixed Pairs: Degenerate–Nondegenerate 136</p> <p>8.6 f Orbitals and Orbital Degeneracy 138</p> <p>References 140</p> <p><b>9 Structure and Properties of p Magnetic Orbitals Systems 143</b></p> <p>9.1 Magnetic Coupling in Organics 143</p> <p>9.2 Magnetism in Nitroxides 145</p> <p>9.3 Thioradicals 147</p> <p>9.4 Metallorganic Magnets 149</p> <p>9.5 Semiquinone Radicals 152</p> <p>9.6 NITR Radicals with Metals 155</p> <p>9.7 Long Distance Interactions in Nitroxides 158</p> <p>References 160</p> <p><b>10 Structure and Properties of Coupled Systems: d, f 163</b></p> <p>10.1 d Orbitals 163</p> <p>10.2 3d 164</p> <p>10.3 4d and 5d 165</p> <p>10.4 Introducing Chirality 169</p> <p>10.5 f-d Interactions 171</p> <p>10.6 A Model DFT Calculation 172</p> <p>10.7 Magneto-Structural Correlations in Gd-Cu 173</p> <p>10.8 f Orbital Systems and Orbital Degeneracy 176</p> <p>References 177</p> <p><b>11 Dynamic Properties 179</b></p> <p>11.1 Introductory Remarks 179</p> <p>11.2 Spin–Lattice Relaxation and T1 181</p> <p>11.3 Phonons and Direct Mechanism 182</p> <p>11.4 Two Is Better than One 185</p> <p>11.5 Playing with Fields 187</p> <p>11.6 Something Real 189</p> <p>11.7 Spin–Spin Relaxation and T2 191</p> <p>References 193</p> <p><b>12 SMM Past and Present 195</b></p> <p>12.1 Mn12, the Start 195</p> <p>12.2 Some Basic Magnetism 198</p> <p>12.3 Fe4 Structure and Magnetic Properties 201</p> <p>12.4 Fe4 Relaxation and Quantum Tunneling 205</p> <p>12.5 And τ0? 207</p> <p>12.6 Deep in the Tunnel 207</p> <p>12.7 Magnetic Dilution Effects 210</p> <p>12.8 Single Molecule Magnetism 211</p> <p>References 213</p> <p><b>13 Single Ion Magnet (SIM) 217</b></p> <p>13.1 Why Single 217</p> <p>13.2 Slow Relaxation in Ho in Inorganic Lattice 218</p> <p>13.3 Quantum Tunneling of the Magnetization: the Role of Nuclei 219</p> <p>13.4 Back to Magnets 222</p> <p>13.5 The Phthalocyanine Family: Some More Chemistry 223</p> <p>13.6 The Anionic Double Decker 224</p> <p>13.7 CF Aspects 225</p> <p>13.8 The Breakthrough 226</p> <p>13.9 Multiple Deckers 229</p> <p>13.10 The Polyoxometalate Family 231</p> <p>13.11 More SIM 233</p> <p>13.12 Perspectives 235</p> <p>References 236</p> <p><b>14 SMM with Lanthanides 239</b></p> <p>14.1 SMM with Lanthanides 239</p> <p>14.2 More Details on SMM with Lanthanides 245</p> <p>14.3 New Opportunities 247</p> <p>References 249</p> <p><b>15 Single Chain Magnets (SCM) and More 251</b></p> <p>15.1 Why 1D 251</p> <p>15.2 The Glauber Model 253</p> <p>15.3 SCM: the d and pWay 257</p> <p>15.4 Spin Glass 259</p> <p>15.5 Noncollinear One-dimensional Systems 260</p> <p>15.6 f Orbitals in Chains: Gd 262</p> <p>15.7 f Orbitals in Chains: Dy 266</p> <p>15.8 Back to Family 271</p> <p>References 274</p> <p><b>16 Magic Dysprosium 277</b></p> <p>16.1 Exploring Single Crystals 277</p> <p>16.2 The Role of Excited States 282</p> <p>16.3 A Comparative Look 289</p> <p>16.4 Dy as a Perturbation 292</p> <p>References 293</p> <p><b>17 Molecular Spintronics 295</b></p> <p>17.1 What? 295</p> <p>17.2 Molecules and Mobile Electrons 297</p> <p>17.3 Of Molecules and Surfaces 302</p> <p>17.4 Choosing Molecules and Surfaces 305</p> <p>17.5 Is it Clean? 307</p> <p>17.6 X-Rays for Magnetism 308</p> <p>17.7 Measuring Magnetism on Surfaces 310</p> <p>17.8 Transport through Single Radicals 311</p> <p>17.9 Pc Family 314</p> <p>17.10 Mn12 Forever 317</p> <p>17.11 Hybrid Organic and f Orbitals 318</p> <p>17.12 Magnetically Active Substrates 319</p> <p>17.13 Using Nuclei 321</p> <p>17.14 Some Device at Last 324</p> <p>References 325</p> <p><b>18 Hunting for Quantum Effects 329</b></p> <p>18.1 From Classic to Quantum 329</p> <p>18.2 Basic QIP 331</p> <p>18.3 A Detour 334</p> <p>18.4 Endohedral Fullerenes 335</p> <p>18.5 Criteria for QIP 338</p> <p>18.6 Starting from Inorganic 340</p> <p>18.7 Molecular Rings 341</p> <p>18.8 V15 346</p> <p>18.9 Qubit Manipulation 347</p> <p>18.10 Some Philosophy 347</p> <p>References 348</p> <p><b>19 Controlling the Growth 351</b></p> <p>19.1 Introduction 351</p> <p>19.2 Metal–Organic Frameworks MOFs 352</p> <p>19.3 From Nano to Giant 358</p> <p>19.4 Molybdates 358</p> <p>19.5 To the Limit 360</p> <p>19.6 Controlling Anisotropy 363</p> <p>19.7 Cluster with Few Lanthanides 365</p> <p>19.8 Analyzing the Magnetic Properties 366</p> <p>19.9 Two-Dimensional Structures 369</p> <p>References 371</p> <p><b>20 ESR 375</b></p> <p>20.1 A Bird’s Eye View of ESR of Ln 375</p> <p>20.2 Gd in Detail 376</p> <p>20.3 Gd with Radicals 379</p> <p>20.4 Including Orbit 381</p> <p>20.5 Involving TM 384</p> <p>20.6 Ln Nicotinates 388</p> <p>20.7 Measuring Distances 391</p> <p>References 392</p> <p><b>21 NMR 395</b></p> <p>21.1 NMR of Rare Earth Nuclides 395</p> <p>21.2 NMR of Lanthanide Ions in Solution 395</p> <p>21.3 Lanthanide Shift Reagents (LSR) 404</p> <p>References 407</p> <p><b>22 Magnetic Resonance Imaging 409</b></p> <p>22.1 Chemical Exchange Saturation Transfer (CEST) 415</p> <p>References 419</p> <p><b>23 Some Applications of MM 421</b></p> <p>23.1 Magnetocaloric Effect 421</p> <p>23.2 Luminescence 424</p> <p>23.2.1 Electroluminescent Materials for OLED 429</p> <p>23.2.2 Biological Assays and Medical Imaging 432</p> <p>References 432</p> <p>Appendix A 435</p> <p>Appendix B 437</p> <p>Index 439</p>
<b>Dante Gatteschi</b> 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. <br /><br /><b>Cristiano Benelli</b> 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.
<p>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<br />useful guide.</p> <p>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.</p> <p>The result is an excellent textbook from both a scientific and pedagogic point of view.</p>

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