『外国名著』Magnetism: Molecules to Materials II

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Contents
1 Nitroxide-based Organic Magnets . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Unconjugated Nitroxides . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.2.1 Mono-nitroxides . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.2.2 Oligo-nitroxides . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.3 Conjugated Nitroxides . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.3.1 Mono-nitroxides . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.3.2 Oligo-nitroxides . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.4 Nitronyl Nitroxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
1.4.1 Mono-nitronyl Nitroxides . . . . . . . . . . . . . . . . . . . . 18
1.4.2 Oligo-nitronyl Nitroxides . . . . . . . . . . . . . . . . . . . . 35
1.4.3 Co-crystallization of Nitronyl Nitroxides . . . . . . . . . . . . 40
1.5 Imino Nitroxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
1.6 Poly(nitroxides) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
1.7 Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2 Magnetic Ordering in Metal Coordination Complexes
with Aminoxyl Radicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
2.2 Aminoxyl Radicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
2.2.1 Electronic Structure and Basicity . . . . . . . . . . . . . . . . 62
2.2.2 Aminoxyl Radicals with Another Basic Center . . . . . . . . 63
2.2.3 High-spin Di- and Poly(aminoxyl) Radicals . . . . . . . . . . 64
2.3 Magnetic Interaction between Transition Metal Ions
and Aminoxyl Radicals . . . . . . . . . . . . . . . . . . . . . . . . . . 65
2.3.1 Indirect Coupling (Extended Superexchange) . . . . . . . . . 65
2.3.2 Complexes with Direct Metal-Aminoxyl Coordination . . . . 70
2.3.3 Cyclic Complexes . . . . . . . . . . . . . . . . . . . . . . . . . 72
2.4 Design Strategy for Various Crystyl Structures . . . . . . . . . . . . . 74
2.5 Preparation of 3d Transition Metal-Poly(aminoxyl)
Radical Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
2.6 One-dimensional Metal-Aminoxyl Systems . . . . . . . . . . . . . . 80
2.6.1 Structure and Magnetic Properties of Ferrimagnetic
1D Chains Formed by Manganese(II) and
Nitronyl Nitroxides . . . . . . . . . . . . . . . . . . . . . . . . 81
Magnetism: Molecules to Materials II: Molecule-Based Materials.
Edited by Joel S. Miller and Marc Drillon
Copyright c 2002Wiley-VCH Verlag GmbH & Co. KGaA
ISBNs: 3-527-30301-4 (Hardback); 3-527-60059-0 (Electronic)
VI Contents
2.6.2 Structure and Magnetic Properties of Ferrimagnetic
1D Chains Formed by Manganese(II) and
Triplet bis-Aminoxyl Radicals . . . . . . . . . . . . . . . . . . 82
2.7 Two-dimensional Metal-Aminoxyl Systems . . . . . . . . . . . . . . . 88
2.7.1 Structure and Magnetic Properties of Ferrimagnetic
2D Sheets Formed by Manganese(II) and
Nitronyl Nitroxides . . . . . . . . . . . . . . . . . . . . . . . . 89
2.7.2 Structure and Magnetic Properties of Ferrimagnetic
2D Sheets Formed by Manganese(II) and
High-spin tris-Aminoxyl Radicals . . . . . . . . . . . . . . . . 90
2.7.3 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
2.8 Three-dimensional Metal-Aminoxyl Systems . . . . . . . . . . . . . . 97
2.8.1 Crystal and Molecular Structure of the 3D System . . . . . . 98
2.8.2 Magnetic Properties of the 3D System . . . . . . . . . . . . . 99
2.8.3 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
2.9 Summary and Prognosis . . . . . . . . . . . . . . . . . . . . . . . . . 104
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
3 Organic Kagome Antiferromagnets . . . . . . . . . . . . . . . . . . . . . . 109
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
3.2 Inorganic Kagome Antiferromagnets . . . . . . . . . . . . . . . . . . 110
3.2.1 SrGa12-xCrxO19 (SCGO(x)) . . . . . . . . . . . . . . . . . . . 110
3.2.2 Jarosite, AM3(OH)6(SO4)2 (A = Na+, K+, Rb+, Ag+, NH+4,
H3O+, etc., and M = Fe3+ or Cr3+) . . . . . . . . . . . . . . . 111
3.3 Organic Kagome Antiferromagnet, m-MPYNN·X . . . . . . . . . . 111
3.3.1 Crystal Structure . . . . . . . . . . . . . . . . . . . . . . . . . 111
3.3.2 Magnetic Susceptibility . . . . . . . . . . . . . . . . . . . . . . 113
3.3.3 Heat Capacity . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
3.3.4 Positive Muon Spin Rotation . . . . . . . . . . . . . . . . . . 116
3.3.5 Distorted Kagome Lattices . . . . . . . . . . . . . . . . . . . . 117
3.3.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
4 Magnetism in TDAE-C60 . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
4.2 Synthesis and Structure . . . . . . . . . . . . . . . . . . . . . . . . . . 124
4.2.1 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
4.2.2 The Lattice Structure . . . . . . . . . . . . . . . . . . . . . . . 126
4.3 The Electronic Structure . . . . . . . . . . . . . . . . . . . . . . . . . 128
4.4 The Magnetic Properties . . . . . . . . . . . . . . . . . . . . . . . . . 130
4.4.1 The Bulk Magnetic Properties . . . . . . . . . . . . . . . . . . 130
4.4.2 The Spin-glass Behavior of α -TDAE-C60 . . . . . . . . . . . 134
4.4.3 Electron-spin Resonance . . . . . . . . . . . . . . . . . . . . . 135
4.4.4 Ferromagnetic Resonance . . . . . . . . . . . . . . . . . . . . 137
4.5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
Contents VII
5 Triarylmethyl and Amine Radicals . . . . . . . . . . . . . . . . . . . . . . 149
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
5.2 Monoradicals (S = 1/2) . . . . . . . . . . . . . . . . . . . . . . . . . . 149
5.3 Diradicals (S=1) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
5.4 Triradicals (S = 3/2) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
5.5 Monodisperse High-spin Oligomers (S=2–ca. 10) . . . . . . . . . . 163
5.6 High-spin Polymers (up to Sn =ca. 48) . . . . . . . . . . . . . . . . . 179
5.7 Conclusions and Prospects (Beyond S = ca. 48?) . . . . . . . . . . . . 182
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
6 High-spin Metal-ion-containing Molecules . . . . . . . . . . . . . . . . . . 189
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
6.2 Self-assembly of Molecular Clusters . . . . . . . . . . . . . . . . . . . 190
6.2.1 Competing Interactions and Spin Frustration . . . . . . . . . 190
6.2.2 The Carboxylate Family . . . . . . . . . . . . . . . . . . . . . 192
6.2.3 The Hydroxypyridonate Family . . . . . . . . . . . . . . . . . 197
6.3 Host-Guest Approach . . . . . . . . . . . . . . . . . . . . . . . . . . 201
6.3.1 Hexanuclear Iron(III) Rings . . . . . . . . . . . . . . . . . . . 202
6.3.2 Hexanuclear Manganese Rings . . . . . . . . . . . . . . . . . 203
6.4 Step-by-step Rationale Approach . . . . . . . . . . . . . . . . . . . . 204
6.4.1 Complex as Ligand and Complex as Metal . . . . . . . . . . . 206
6.4.2 Predicting the Spin Ground State . . . . . . . . . . . . . . . . 207
6.4.3 Antiferromagnetic Approach . . . . . . . . . . . . . . . . . . 208
6.4.4 Ferromagnetic Approach . . . . . . . . . . . . . . . . . . . . . 211
6.4.5 Role of the Organic Ligand . . . . . . . . . . . . . . . . . . . 214
6.4.6 Molecules with Two Shells of Paramagnetic Species . . . . . 217
6.5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
7 Electronic Structure and Magnetic Behavior
in Polynuclear Transition-metal Compounds . . . . . . . . . . . . . . . . . 227
7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
7.2 Phenomenological Description of Exchange Coupling:
the Heisenberg Hamiltonian . . . . . . . . . . . . . . . . . . . . . . . 228
7.3 Qualitative Models of the Exchange Coupling Mechanism . . . . . . 230
7.3.1 Orthogonal Magnetic Orbitals . . . . . . . . . . . . . . . . . . 230
7.3.2 Natural Magnetic Orbitals . . . . . . . . . . . . . . . . . . . . 234
7.4 Quantitative Evaluation of Exchange Coupling Constants . . . . . . 235
7.4.1 Perturbative and Variational Calculations
of State Energy Differences . . . . . . . . . . . . . . . . . . . 236
7.4.2 Ab initio Calculations of State Energies . . . . . . . . . . . . 240
7.4.3 Calculations using Broken-symmetry Functions . . . . . . . . 242
7.5 Exchange Coupling in Polynuclear Transition-metal Complexes . . . 249
7.5.1 Homodinuclear Compounds . . . . . . . . . . . . . . . . . . . 249
7.5.2 Heterodinuclear Compounds . . . . . . . . . . . . . . . . . . 261
VIII Contents
7.5.3 Polynuclear Compounds . . . . . . . . . . . . . . . . . . . . . 263
7.5.4 Solid-state Compounds: The Case of Cu2(OH)3NO3 . . . . . 266
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271
8 Valence Tautomerism in Dioxolene Complexes of Cobalt . . . . . . . . . 281
8.1 Introduction – Bistability, Hysteresis,
and Electronically Labile Materials . . . . . . . . . . . . . . . . . . . 281
8.1.1 Bistability and Hysteresis . . . . . . . . . . . . . . . . . . . . 281
8.1.2 Electronically Labile Materials . . . . . . . . . . . . . . . . . 281
8.2 Valence Tautomerism in Dioxolene Complexes of Cobalt . . . . . . 284
8.2.1 Valence Tautomerism – A General Chemical Description . . 284
8.2.2 Valence Tautomerism – A Simplified MO Description . . . . 287
8.2.3 VT Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . 288
8.2.4 Experimental Determination of Thermodynamic Parameters 290
8.2.5 Dependence of KVT Equilibrium on Ancillary Ligands . . . 292
8.2.6 Pressure-induced VT . . . . . . . . . . . . . . . . . . . . . . . 297
8.2.7 Light-induced VT and Rates of VT . . . . . . . . . . . . . . . 299
8.2.8 VT Complexes of Other Quinone Ligands
and Redox Chemistry of VT Complexes . . . . . . . . . . . . 300
8.2.9 Polymeric VT Materials . . . . . . . . . . . . . . . . . . . . . 302
8.3 Future Directions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 304
9 Molecule-based Magnets Derived from NiII and MnII
Azido Bridging Ligand and Related Compounds . . . . . . . . . . . . . . 307
9.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 307
9.2 Synthetic Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
9.3 Exchange-coupling Parameter . . . . . . . . . . . . . . . . . . . . . . 309
9.4 Molecular-based Magnetic Materials . . . . . . . . . . . . . . . . . . 309
9.5 One-dimensional Systems . . . . . . . . . . . . . . . . . . . . . . . . 312
9.5.1 With 1,3-Azido Bridging Ligands (AF, Uniform) . . . . . . . 312
9.5.2 With 1,3-Azido Bridging Ligands (AF, Alternating) . . . . . 313
9.5.3 With 1,1-Azido Bridging Ligands (Ferromagnetic) . . . . . . 316
9.5.4 With 1,3-N3 and 1,1-N3 bridges . . . . . . . . . . . . . . . . . 319
9.6 Two-dimensional Systems . . . . . . . . . . . . . . . . . . . . . . . . . 322
9.6.1 With Only Azido as Bridging Ligand . . . . . . . . . . . . . . 322
9.7 Three-dimensional Systems . . . . . . . . . . . . . . . . . . . . . . . . 329
9.8 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 334
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335
10 Oxalate-based 2D and 3D Magnets . . . . . . . . . . . . . . . . . . . . . . 339
10.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
10.2 Basic Principles of Specific 2D and 3D Network Configurations . . . 339
10.3 Structural Studies on 2D Oxalato Bridged Compounds . . . . . . . . 344
10.4 Magnetic Studies on 2D Oxalato Bridged Compounds . . . . . . . . 346
10.5 Structural Studies on 3D Oxalato Bridged Compounds . . . . . . . . 349
Contents IX
10.6 Magnetic Studies on 3D Oxalato Bridged Compounds . . . . . . . . 352
10.7 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
11 Hybrid Organic-Inorganic Multilayer Compounds:
Towards Controllable and/or Switchable Magnets . . . . . . . . . . . . . . 357
11.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
11.2 Hydroxide-based Layered Compounds . . . . . . . . . . . . . . . . . 358
11.3 Anion-exchange Reactions . . . . . . . . . . . . . . . . . . . . . . . . 360
11.4 Influence of Organic Spacers in Hydroxide-based Compounds . . . . 361
11.4.1 The Cu2(OH)3X Series . . . . . . . . . . . . . . . . . . . . . . 361
11.4.2 The Co2(OH)3X Series . . . . . . . . . . . . . . . . . . . . . . 364
11.4.3 Dipolar Interaction and Long-range Magnetic Order . . . . . 367
11.5 Difunctional Organic Anions Connecting Magnetic Layers . . . . . . 370
11.6 Metal-radical-based Layered Magnets . . . . . . . . . . . . . . . . . 376
11.7 Controllable Magnetic Properties of Layered Copper Hydroxides . . 380
11.7.1 Solvent-mediated Magnetism . . . . . . . . . . . . . . . . . . 380
11.7.2 Photoisomerism of Azobenzenes
in Layered Copper Hydroxides . . . . . . . . . . . . . . . . . 384
11.8 Layered Perovskite Ferromagnets . . . . . . . . . . . . . . . . . . . . 385
11.8.1 High-pressure Effects . . . . . . . . . . . . . . . . . . . . . . . 386
11.8.2 Spontaneous Magnetization
in Layered Perovskite Ferromagnets . . . . . . . . . . . . . . 389
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393
12 Intercalation-induced Magnetization
in MPS3 Layered Compounds . . . . . . . . . . . . . . . . . . . . . . . . . 397
12.1 Introduction and Scope . . . . . . . . . . . . . . . . . . . . . . . . . . 397
12.2 Structural and Electronic Aspects . . . . . . . . . . . . . . . . . . . . 397
12.3 Magnetic Properties of the Pristine MPS3 Phases (M = Mn, Fe, Ni) . 399
12.4 Ion-exchange Intercalation into the MPS3 Compounds . . . . . . . . 401
12.5 The Magnetic Properties of the MnPS3 Intercalates . . . . . . . . . . 402
12.5.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 402
12.5.2 X-ray and Neutron-diffraction Study
of Selected Intercalates . . . . . . . . . . . . . . . . . . . . . . 405
12.5.3 A Ferrimagnetic Model of the MnPS3 Intercalates:
Imbalancing of Spins . . . . . . . . . . . . . . . . . . . . . . . 407
12.6 The Magnetic Properties of the FePS3 Intercalates . . . . . . . . . . 410
12.6.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410
12.6.2 Spectroscopic Characterization of the FePS3 Intercalates . . 413
12.6.3 Discussion on the Role of Intercalation into FePS3 . . . . . . 415
12.6.4 Magnetic Properties of Iron-diluted
Fe1−xCdxPS3 Compounds . . . . . . . . . . . . . . . . . . . . 416
12.6.5 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 417
12.7 The NiPS3-Cobaltocene Intercalation Compound . . . . . . . . . . . 419
X Contents
12.8 Multi-property Materials:
Associating Magnetism and Non-linear Optics . . . . . . . . . . . . . 420
12.9 Conclusion and Perspectives . . . . . . . . . . . . . . . . . . . . . . . 421
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 421
13 Transition Metal Ion Phosphonates
as Hybrid Organic–Inorganic Magnets . . . . . . . . . . . . . . . . . . . . 425
13.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
13.2 Synthesis of the Ligands . . . . . . . . . . . . . . . . . . . . . . . . . 426
13.3 Vanadium Phosphonates . . . . . . . . . . . . . . . . . . . . . . . . . 426
13.3.1 Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 426
13.3.2 Crystal Structures . . . . . . . . . . . . . . . . . . . . . . . . . 427
13.3.3 Magnetic Properties . . . . . . . . . . . . . . . . . . . . . . . 427
13.4 Divalent Metal Phosphonates . . . . . . . . . . . . . . . . . . . . . . 430
13.4.1 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 430
13.4.2 Crystal Structures . . . . . . . . . . . . . . . . . . . . . . . . . 432
13.4.3 Magnetic Properties . . . . . . . . . . . . . . . . . . . . . . . 437
13.5 Metal(II) Diphosphonates . . . . . . . . . . . . . . . . . . . . . . . . 449
13.5.1 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 449
13.5.2 Crystal Structures . . . . . . . . . . . . . . . . . . . . . . . . . 450
13.5.3 Magnetic Properties . . . . . . . . . . . . . . . . . . . . . . . 452
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 454
14 Magnetic Langmuir-Blodgett Films . . . . . . . . . . . . . . . . . . . . . . 457
14.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457
14.2 The Langmuir–Blodgett Technique . . . . . . . . . . . . . . . . . . . 459
14.2.1 Fabrication of Langmuir–Blodgett Films . . . . . . . . . . . . 459
14.2.2 Structural and Physical Characterization
of Langmuir and LB Films . . . . . . . . . . . . . . . . . . . . 461
14.3 Magnetic Systems: A Molecular Approach . . . . . . . . . . . . . . . 462
14.3.1 Hybrid LB Films with Magnetic Clusters . . . . . . . . . . . . 462
14.3.2 Spin-transition Systems . . . . . . . . . . . . . . . . . . . . . . 465
14.3.3 Comments on Molecular Magnetism in LB Films . . . . . . . 468
14.4 Extended Systems and Cooperative Effects . . . . . . . . . . . . . . 469
14.4.1 “Literally Two-Dimensional Magnets” . . . . . . . . . . . . . 469
14.4.2 Metal Phosphonate LB Films . . . . . . . . . . . . . . . . . . 470
14.4.3 Organic and Inorganic “Dual Network” Films . . . . . . . . . 473
14.4.4 Bimetallic Compounds . . . . . . . . . . . . . . . . . . . . . . 475
14.5 Comparison with Other Lamellar and Colloidal Systems . . . . . . . 478
14.5.1 Hybrid Lamellar Systems . . . . . . . . . . . . . . . . . . . . 479
14.5.2 Self-organized Media . . . . . . . . . . . . . . . . . . . . . . . 480
14.6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 481
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 482
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 485

[ 本帖最后由 wmwmwm 于 2008-10-24 08:13 编辑 ]