Molecular magnetic materials: concepts and applications

496 Pages·2016·17.164 MB·English

by  Pinkowicz, Dawid, Sieklucka, Barbara

Editedby
BarbaraSiekluckaand
DawidPinkowicz
MolecularMagneticMaterials
EditedbyBarbaraSiekluckaandDawidPinkowicz
Molecular Magnetic Materials
ConceptsandApplications
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FrontcoverpresentsaCo Fe molecule Bibliographicinformationpublishedbythe
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V
Contents
ListofContributors XV
Preface XXI
1 Magnetism 1
MariaBałandaandRobertPełka
1.1 OriginofMagnetism 1
1.2 MacroscopicApproach 3
1.3 UnitsinMagnetism 5
1.4 GroundStateofanIonandHund’sRules 6
1.5 AnAtominaMagneticField 9
1.6 MechanismsofMagneticInteractions 10
1.6.1 DipolarInteractions 11
1.6.2 DirectExchange 11
1.6.3 IndirectExchange–Superexchange 12
1.6.4 IndirectExchange–DoubleExchange 13
1.6.5 IndirectExchange–AntisymmetricExchange 14
1.6.6 ItinerantExchange–RKKYInteraction 14
1.6.7 MagnetismofItinerantElectrons 15
1.7 CollectiveMagneticState 17
1.7.1 ModelsofInteractionandDimensionoftheLattice 17
1.7.2 Ferromagnets 18
1.7.3 Antiferromagnets 20
1.7.4 Ferrimagnets 22
1.7.5 SpinGlasses 23
1.7.6 Superparamagnets 25
1.8 ApplicationsandResearch 26
References 28
2 MolecularMagnetism 29
MichaelShatruk,SilviaGómez-Coca,andKimR.Dunbar
2.1 Introduction 29
2.2 BirthoftheTopic:Exchange-CoupledClusters 29
2.3 EvolutionoftheTopic:Molecule-BasedMagnets 31
VI Contents
2.4 BurgeoningTopics:Single-MoleculeMagnets 32
2.5 Single-ChainMagnets 37
2.6 SpinCrossoverComplexes 40
2.7 ChargeTransfer-InducedSpinTransitions 43
2.8 MultifunctionalMaterials 44
2.9 FuturePerspectives 46
References 48
3 High-SpinMolecules 53
Zhao-PingNiandMing-LiangTong
3.1 Introduction 53
3.2 StrategiesforHigh-SpinMolecules 54
3.2.1 MagneticExchangeStrategyforHigh-SpinMolecules 54
3.2.1.1 StrictOrthogonalityoftheMagneticOrbitalsforFerromagnetic
Interaction 54
3.2.1.2 AccidentalOrthogonalityoftheMagneticOrbitalsfor
FerromagneticInteraction 56
3.2.1.3 SpinPolarizationMechanismforFerromagneticInteraction 57
3.2.2 SyntheticStrategyforHigh-SpinMolecules 58
3.2.2.1 BridgingLigandsforHigh-SpinMolecules 58
3.2.2.2 TheEffectoftheBlockingLigands 60
3.3 High-SpinMoleculesbasedond-MetalIons 60
3.3.1 Homo-MetallicHigh-SpinMoleculesbasedond-MetalIons 61
3.3.2 Hetero-MetallicHigh-SpinMoleculesBasedond-Metal
Ions 66
3.4 High-SpinMoleculesBasedonf-MetalIons 67
3.5 High-SpinMoleculesBasedond–fMetalIons 69
3.6 ConclusionsandPerspectives 71
References 72
4 SingleMoleculeMagnets 79
MasahiroYamashitaandKeiichiKatoh
4.1 Introduction 79
4.1.1 MolecularMagnets 79
4.1.2 RoughOutlineoftheSingle-MoleculeMagnets(SMMs) 79
4.2 MeasurementTechniques 82
4.2.1 DirectCurrent(dc)Measurements 82
4.2.2 RemnantMagnetization 85
4.2.3 AlternatingCurrent(ac)Measurements 86
4.2.4 ElectronSpinResonance(ESR) 88
4.2.5 NuclearMagneticResonance(NMR) 89
4.2.6 OtherMethods 91
4.3 RationalDesignofSMMs 91
4.4 FamilyofSMMs 93
4.4.1 PolynucleardMetalComplexes 93
Contents VII
4.4.2 MononucleardMetalcomplexes(Single-IonMagnets(SIMs)) 95
4.4.3 MononuclearfMetalComplexes(SIMs) 95
4.4.4 PolynuclearfMetalComplexes 96
4.4.5 MixedMetalnd–4fComplexes 97
4.5 ConclusionsandPerspectives 97
References 98
5 MagneticMoleculesasSpinQubits 103
PaoloSantini,StefanoCarretta,andGiuseppeAmoretti
5.1 Introduction 103
5.1.1 QIPParadigmswithMagneticMolecules 105
5.2 MolecularQubits 107
5.3 SchemesforTwo-QubitGates 110
5.3.1 PermanentlyCoupledQubits 110
5.3.2 SwitchableEffectiveInteractionsintheLackofLocal
Control 112
5.3.3 QuantumSimulations 116
5.3.4 TheCr Ni–Ni–Cr NiSupramolecularComplexes 118
7 7
5.3.5 ImplementationofTwo-QubitGateswithaTip 122
5.4 ConclusionsandPerspectives 123
Appendix:TheBasics 125
ListofAcronyms 127
References 127
6 Single-ChainMagnets 131
KasperS.Pedersen,AlessandroVindigni,RobertaSessoli,ClaudeCoulon,and
RodolpheClérac
6.1 Introduction 131
6.2 TheVeryBasics 132
6.3 SyntheticEndeavorsTowardSCMs 135
6.3.1 TheDawnofSCMs:TheMetal–RadicalApproach 136
6.3.2 UsingPredesignedBuildingBlocks:TowardMagneticallyOrdered
SystemsandCantedSCMs 137
6.3.3 BenefittingfromHeavyMetalIonsandOrbitalAngular
Momenta 140
6.4 TheoreticalModeling 141
6.4.1 ClassicalSpinApproachtoDescribeSCMSystems 142
6.4.2 SystemswithNoncollinearAnisotropyAxes 147
6.5 NewDirections 150
6.5.1 TowardLight-inducedSCMs 150
6.5.2 ExternalControlofSpinDynamicsinSCM 151
6.5.3 MultifunctionalSCMs:Magnetochirality 153
6.6 ConclusionsandPerspectives 155
References 156
VIII Contents
7 High-T OrderedMolecularMagnets 161
c
JoelS.MillerandShin-ichiOhkoshi
7.1 Introduction 161
7.2 TCNE-BasedMolecule-BasedMagnets 163
7.3 PrussianBlueAnalogs 168
7.4 Hepta-andOctacyanido-basedMolecule-basedMagnets 174
7.5 ConclusionsandPerspectives 180
References 182
8 ThinLayersofMolecularMagnets 187
AndreaCornia,DanielR.Talham,andMarcoAffronte
8.1 IntroductoryRemarks 187
8.2 ThinLayersofSingle-MoleculeMagnets 188
8.2.1 ClassesofSingle-MoleculeMagnets 188
8.2.2 ProcessingMethodsforThinLayersofSingle-Molecule
Magnets 191
8.2.3 ProbingMagnetisminThinLayersofSingle-Molecule
Magnets 193
8.2.4 One-Molecule-ThickLayersofSingle-MoleculeMagnets 194
8.2.4.1 RoleoftheSurface:LessonsLearnedfromSimpleSystems 194
8.2.4.2 RoleoftheSurface:SMM-SpecificEffects 196
8.2.4.3 SummaryofEarlyFindings 197
8.2.4.4 Fe Propellers 198
4
8.2.4.5 LnPc Series 200
2
8.2.4.6 Ln(trensal)ComplexesandEndofullerenes 204
8.2.5 MultilayersandSubmicronFilmsofSingle-MoleculeMagnets 204
8.3 ThinLayersofAntiferromagneticSpinClusters 206
8.4 ThinLayersofHigh-SpinCages 209
8.5 ThinLayersofMolecularMagnetswithExtendedNetworks 211
8.5.1 Langmuir–BlodgettFilms 211
8.5.2 CyanometallateFilms 213
8.5.3 V(TCNE) andDerivatives 214
x
8.5.4 SpinCrossoverNetworks 216
8.5.5 Heterostructures 217
8.6 ConclusionsandPerspectives 218
Acknowledgments 220
References 220
9 SpinCrossoverPhenomenoninCoordinationCompounds 231
AnaB.GasparandBirgitWeber
9.1 Introduction 231
9.2 SpinCrossoverintheSolidandLiquidStates 232
9.2.1 FollowingSpinTransitionsinSolution 233
9.2.2 Hysteresis 233
9.2.3 EffectofScanRate 235
Contents IX
9.2.4 StepwiseSpinTransitions 235
9.3 MultifunctionalityinSpinCrossoverCompounds 236
9.4 SpinCrossoverPhenomenoninSoftMatter 238
9.5 SpincrossoverPhenomenonattheNanoscale 239
9.6 ChargeTransportPropertiesofSingle-SpinCrossover
Molecules 245
9.7 Conclusion 245
References 246
10 PorousMolecularMagnets 253
Wei-XiongZhang,Ming-HuaZeng,andXiao-MingChen
10.1 Introduction 253
10.2 PMMswithSpin-StateSwitching 255
10.3 PMMswithSlowRelaxationofMagnetization 258
10.3.1 PMMswithSMMDynamics 259
10.3.2 PMMswithSpinGlass-likeBehaviors 260
10.3.3 PMMswithSCMDynamics 263
10.4 PMMswithLong-RangeMagneticOrdering 264
10.4.1 3DNetworkApproach 264
10.4.2 2DMagneticLayerApproach 266
10.4.2.1 Pillared-LayerMagnets 266
10.4.2.2 LayerMagnetsbasedon4d–5dIons 268
10.4.2.3 LayerMagnetsbasedonChargeTransferSystem 268
10.4.3 1DMagneticChainApproach 269
10.5 PMMswithSwitchingBetweenFerromagnetismand
Antiferromagnetism 271
10.6 PMMswiththeMagnetism-ModifiedThroughPostsynthetic
Process 273
10.7 ConclusionsandPerspectives 275
References 276
11 MolecularMagneticSponges 279
DawidPinkowicz,RobetPodgajny,andBarbaraSieklucka
11.1 Introduction 279
11.2 TheFirstMolecularMagneticSpongeSystems 281
11.3 CN-BridgedMolecularMagneticSponges 283
11.3.1 Low-DimensionalCN-BridgedMolecularMagneticSponges 284
11.3.2 CN-BridgedMolecularMagneticSpongeswith2D→3D
Transformation 286
11.3.3 CN-BridgedMolecularMagneticSpongeswith3D→3D
Transformation 288
11.3.4 OntheBorderlineofMicroporosityandMagneticSpongeBehavior
inCN-BridgedSystems 292
11.4 MolecularMagneticSpongeswithBridgingLigandsOtherThan
Cyanide 294
X Contents
11.5 ConclusionsandPerspectives 296
References 297
12 Non-CentrosymmetricMolecularMagnets 301
CyrilleTrain,GeertRikken,andMichelVerdaguer
12.1 Introduction 301
12.1.1 ScopeoftheChapter 301
12.1.2 EffectofSymmetryonPhysicalProperties 302
12.1.3 DimensionalityoftheCoordination-BondedMolecular
Objects 304
12.2 SyntheticStrategiesTowardNon-centrosymmetricMagnets
(NCM) 304
12.2.1 SpontaneousCrystallizationinNon-centrosymmetricSpace
Groups 305
12.2.2 UsingChiralLigands 307
12.2.3 EnantioselectiveSelf-Assembly 310
12.3 PhysicochemicalPropertiesofNon-centrosymmetricMagnets 311
12.3.1 SpecificMagneticProperties 312
12.3.2 MSHG 313
12.3.3 MChD 315
12.3.4 Multiferroicity 316
12.4 Conclusion 319
Acknowledgment 319
References 319
13 MolecularPhotomagnets 323
CorineMathonière,HirokoTokoro,andShin-ichiOhkoshi
13.1 Introduction 323
13.2 PhotomagneticCoordinationNetworksbasedon[M(CN) ]
x
(x=6or8) 325
13.2.1 Hexacyanidometallate-BasedPhotomagnets 325
13.2.1.1 PhotoinducedMagneticPoleInversioninaFerro–Ferrimagnet
(FeII0.40MnII0.60)1.5[CrIII(CN)6] 326
13.2.1.2 Antiferro–FerromagneticPhotoswitchinginaMultifunctional
Magnet,RbIMnII[FeIII(CN) ] 327
6
13.2.1.3 PhotoinducedMagnetizationinCoII [OsIII(CN) ] ⋅6H OPrussian
3 6 2 2
BlueAnalog 329
13.2.1.4 PhotoinducedMagnetizationinHeterostructuresofPrussianBlue
Analogs 329
13.2.2 Octacyanidometallate-BasedPhotomagnets 330
13.2.2.1 Copper(II)–Octacyanomolybdate(IV)Systems 330
13.2.2.2 Cobalt(II)–Octacyanotungstate(V)Systems 331
13.3 PhotomagneticPolynuclearMoleculesBasedon[M(CN) ]
x
(x=6or8) 333