Spin-Crossover Materials: Properties and Applications

562 Pages·2013·16.559 MB·English

Spin-Crossover Materials
Spin-Crossover Materials
Properties and Applications
Editedby
MALCOLMA.HALCROW
SchoolofChemistry,UniversityofLeeds,UK
A John Wiley & Sons, Ltd., Publication
Thiseditionfirstpublished2013
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Contents
ListofContributors xv
Preface xvii
1 TheDevelopmentofSpin-CrossoverResearch 1
KeithS.Murray
1.1 Introduction 1
1.2 DiscreteClustersofSCOCompounds 4
1.2.1 DinuclearFeII-FeII SCOClusters 6
1.2.2 Tri-,Tetra-,Penta-andHexa-nuclearFeIISCOClusters 18
1.3 1DChainsofFeIISCOMaterials 22
1.4 1DChainsofFeIIISCOMaterials 28
1.5 2DSheetsofFeII SCOMaterials 29
1.6 3DPorousSCOMaterials 30
1.7 SomeRecentDevelopmentsinMononuclearSCOFeII,FeIIIandCoIICompounds 33
1.7.1 Iron(II)andIron(III) 33
1.7.2 Cobalt(II) 35
1.8 Multifunctional/HybridSCOMaterials 37
1.8.1 SCOandPorosity 38
1.8.2 SCOandElectricalConductivity 38
1.8.3 SCOand(i)Short-RangeExchangeCouplingor(ii)Long-RangeMagneticOrder 38
1.8.4 SCOandLiquidCrystals 39
1.8.5 SCOandGels 39
1.8.6 SCOandNLO 39
1.9 DevelopmentsinInstrumentalMethodsinSpin-CrossoverMeasurements 40
1.10 ApplicationsofMolecularSpin-CrossoverCompounds 41
1.11 Summary 42
Acknowledgements 42
References 43
2 NovelMononuclearSpin-CrossoverComplexes 55
BirgitWeber
2.1 IntroductionandGeneralConsiderations 55
2.2 NovelCoordinationNumbers(CN),CoordinationGeometriesandMetalCentres 57
2.2.1 CoordinationNumber7 57
2.2.2 CoordinationNumber6 58
2.2.3 CoordinationNumber5 60
2.2.4 CoordinationNumber4+1 62
2.2.5 CoordinationNumber4 63
vi Contents
2.3 IronComplexeswithNovelLigandDonorAtomsandNewLigandSystems 65
2.3.1 N CoordinationSphere 65
6
2.3.2 N O CoordinationSphere 66
4 2
2.4 OtherExamples 70
2.5 ConclusionandOutlook 72
References 72
3 Spin-CrossoverinDiscretePolynuclearComplexes 77
JuanOlgu´ınandSallyBrooker
3.1 Introduction 77
3.2 DinuclearIron(II)Complexes 79
3.2.1 SupramolecularApproach 79
3.2.2 ‘Controlled/Designer-Ligand’Approach 84
3.2.3 LigandswithTwoIsolatedBindingPockets 84
3.2.4 LigandswithPotentialforCommunicationbetweenBindingPockets 91
3.3 HigherNuclearityIron(II)Compounds 98
3.3.1 TrinuclearIron(II)Complexes 98
3.3.2 TetranuclearIron(II)Complexes 100
3.3.3 HigherNuclearityMixedMetal/ValentIron(II)Complexes 103
3.4 Iron(III) 104
3.4.1 DinuclearIron(III)Complexes 104
3.4.2 MixedMetalIron(III)Complexes 108
3.4.3 MixedValenceIron(II)/(III)Complexes 108
3.5 Cobalt(II) 109
3.5.1 DinuclearCobalt(II)Complexes 109
3.5.2 TrinuclearCobalt(II)Complexes 110
3.6 DinuclearChromium(II)Complex 111
3.7 ConcludingRemarks 112
References 113
4 PolymericSpin-CrossoverMaterials 121
M.CarmenMun˜ozandJose´ AntonioReal
4.1 Introduction 121
4.2 One-DimensionalSCO-CPs 121
4.2.1 TriazoleBasedBridges 121
4.2.2 TetrazoleBasedBridges 124
4.2.3 Bis-MonodentatePyridine-LikeBridges 124
4.2.4 PolydentateChelateBridges 126
4.2.5 AnionicBridgingLigands 127
4.3 TwoDimensionalSCO-CPs 128
4.3.1 NeutralOrganicBridgingLigands 128
4.3.2 Dicyanometalate[MI(CN) ]–BridgingLigands(MI=Cu,Ag,Au) 130
2
4.3.3 Tetracyanometalate[MII(CN) ]2–BridgingLigands(MII=Ni,Pd,Pt) 132
4
4.4 Three-DimensionalSCO-CPs 133
4.4.1 NeutralOrganicBridgingLigands 133
4.4.2 Dicyanometalate[MI(CN) ]–BridgingLigands 134
2
Contents vii
4.4.3 Tetracyanometalate[MII(CN) ]2–BridgingLigands 136
4
4.4.4 Hexa-andOctacyano-metallateBridgingLigands 137
4.5 Conclusion 138
Acknowledgement 138
References 139
5 Structure:FunctionRelationshipsinMolecularSpin-CrossoverMaterials 147
MalcolmA.Halcrow
5.1 Introduction 147
5.2 MolecularShape 150
5.2.1 MolecularShapeInducingCooperativity 153
5.2.2 MolecularShapeInhibitingSpin-Crossover 154
5.3 CrystalPacking 155
5.3.1 ShortIntermolecularContacts 156
5.3.2 InhibitionofSpin-CrossoverbyStericCongestion 157
5.4 CooperativityMediatedbyDisorder 158
5.5 CompoundsShowingWideThermalHysteresis 158
5.5.1 CompoundswithSymmetricHysteresisLoops 159
5.5.2 CompoundswithStructuredHysteresisLoops 161
5.6 OtherNoteworthyCompounds 162
5.6.1 Iron(II)TriazoleCoordinationPolymers 162
5.6.2 CooperativeComplexesofOtherMetalIons 163
5.7 Conclusions 164
References 164
6 ChargeTransfer-InducedSpin-TransitionsinCyanometallateMaterials 171
KimR.Dunbar,CatalinaAchimandMichaelShatruk
6.1 Introduction 171
6.2 CharacterizationofCTISTCompounds 173
6.3 CTISTinCoordinationPolymers 174
6.3.1 Co-FePrussianBlueAnalogs 174
6.3.2 OtherPrussianBlueAnalogs 183
6.3.3 CoordinationPolymersBasedonOctacyanometallates 185
6.4 CTISTinNanoscaleMaterials 189
6.4.1 ThinFilms 189
6.4.2 Nanoparticles 192
6.5 CTISTinPolynuclearTransitionMetalComplexes 195
6.6 SummaryandOutlook 198
Acknowledgement 199
References 199
7 ValenceTautomericTransitionsinCobalt-dioxoleneComplexes 203
ColetteBoskovic
7.1 Introduction 203
7.2 InductionofValenceTautomericTransitions 205
7.2.1 ThermallyInducedValenceTautomerism 205
7.2.2 PressureInducedValenceTautomerism 205
viii Contents
7.2.3 LightInducedValenceTautomerism 207
7.2.4 MagneticFieldInducedValenceTautomerism 208
7.2.5 X-RayInducedValenceTautomerism 209
7.3 OtherFactorsthatContributetotheValenceTautomericTransition 210
7.3.1 AncillaryLigandEffects 210
7.3.2 CounterionandSolvationEffects 210
7.3.3 Cooperativity 212
7.3.4 ValenceTautomerisminSolution 214
7.4 PolynuclearValenceTautomericComplexes 214
7.4.1 DinuclearValenceTautomericComplexes 214
7.4.2 PolymericValenceTautomericComplexes 217
7.5 BifunctionalValenceTautomericComplexes 218
7.6 ConcludingRemarks 220
Acknowledgements 221
References 221
8 ReversibleSpinPairinginCrystallineOrganicRadicals 225
JeremyM.RawsonandJohnJ.Hayward
8.1 Introduction 225
8.2 RadicalPairs:SolutionandGasPhaseStudies 226
8.2.1 RadicalDimerisationinSolution 226
8.2.2 ComputationalStudiesonDimerisation 226
8.3 DimerisationintheSolidState 229
8.3.1 StructuralStudies 229
8.3.2 ElectronicStructureandBonding 229
8.3.3 ThermallyAccessibleTripletStates 230
8.3.4 Spin-TransitionRadicalDimers 230
8.3.5 Trithiatriazinyl,TTTA:ACaseStudy 233
8.4 SummaryandFuturePerspectives 234
Acknowledgements 235
References 235
9 BreathingCrystalsfromCopperNitroxylComplexes 239
VictorOvcharenkoandElenaBagryanskaya
9.1 Introduction 239
9.2 StructuralandMagneticAnomalies 241
9.3 RelationshipbetweentheChemicalStepandthePhysicalProperty 245
9.4 RelationshipbetweentheThermallyInducedReorientationofAromaticSolvate
MoleculesandtheCharacteroftheMagneticAnomaly 251
9.5 EPRStudyofBreathingCrystals 255
9.5.1 GeneralTrendsofEPRofStronglyExchange-coupledSpinTriads 256
9.5.2 PredominantPopulationoftheGroundMultiplet 257
9.5.3 DynamicSpinExchangeProcesses 259
9.6 ClassificationofSpin-TransitionsinBreathingCrystalsandCorrelations
withMagneticSusceptibility 261
Contents ix
9.7 TheDetailedMagneticStructureofBreathingCrystals 266
9.7.1 EPRMeasurementsofTemperatureDependenceofIntra-cluster
ExchangeInteraction 266
9.7.2 EPRMeasurementofDipole–DipoleInteractionandInter-cluster
ExchangeInteraction 268
9.8 EPR-detectedLIESSTonBreathingCrystals 272
9.9 Conclusion 275
References 276
10 Spin-StateSwitchinginSolution 281
MatthewP.Shores,ChristinaM.KlugandStephanieR.Fiedler
10.1 IntroductionandScope 281
10.2 Spin-Crossover:SolidStateVersusSolution 282
10.3 PracticalConsiderations 283
10.3.1 NMRCharacterization 283
10.3.2 SQUIDMagnetometry 285
10.3.3 ElectronicAbsorptionSpectroscopy 285
10.4 Spin-CrossoverinSolution 285
10.4.1 SolutionCharacterization 285
10.4.2 SolventEffects 287
10.4.3 SubstituentEffects 288
10.5 LigationChangesDrivingSpin-StateSwitchinginSolution 288
10.5.1 SolventExchange/Loss 288
10.5.2 AnionExchange/Loss 289
10.5.3 (Photo)Isomerization 290
10.5.4 Encapsulation 291
10.6 SecondCoordinationSphereTriggersforSpin-StateSwitching 291
10.6.1 ExternalAnion-DependentSpinSwitching 293
10.6.2 UsingLigandFieldstoTuneAnionTriggeredSpin-StateSwitching
inSolution 293
10.7 ChallengesandOpportunities 294
10.7.1 NewOpportunitiesforAnionReportinginSolution 294
10.7.2 MRIContrast 295
10.8 Conclusions/Outlook 295
Acknowledgement 295
Abbreviations 295
References 296
11 MultifunctionalMaterialsCombiningSpin-CrossoverwithConductivity
andMagneticOrdering 303
OsamuSato,Zhao-YangLi,Zi-ShuoYao,SoonchulKangandShinjiKanegawa
11.1 Introduction 303
11.2 Spin-CrossoverandConductivity:Spin-CrossoverConductors 303
11.2.1 Conclusions 308
11.3 Spin-CrossoverandMagneticInteraction:Spin-CrossoverMagnets 308
11.3.1 HybridSpin-CrossoverCationandAnionicMagneticFramework 308
x Contents
11.3.2 IncorporationofSpin-CrossoverSitesinaMagneticFramework 310
11.3.3 Conclusion 316
References 316
12 AmphiphilicandLiquidCrystallineSpin-CrossoverComplexes 321
ShinyaHayami
12.1 Introduction 321
12.2 UniqueMagneticPropertiesofSCOCobalt(II)CompoundswithLongAlkylChains 322
12.2.1 ReverseSpin-TransitionforCobalt(II)Compounds 322
12.2.2 Re-EntrantSpin-TransitionforCobalt(II)Compounds 324
12.3 LiquidCrystallineSCOCompounds 325
12.3.1 MetallomesogenswithSCOProperty 326
12.3.2 SynchronizationofSCOandLiquidCrystalTransition 327
12.4 Langmuir–BlodgettFilmsandAmphiphilicSCOCompounds 331
12.4.1 SCOLangmuir–BlodgettFilms 332
12.4.2 AmphiphilicSCOCompounds 333
12.5 ConclusionandOutlook 339
References 340
13 LuminescentSpin-CrossoverMaterials 347
HelenaJ.Shepherd,CarlosM.Quintero,Ga´borMolna´r,LionelSalmon
andAzzedineBousseksou
13.1 GeneralIntroduction 347
13.2 IntroductiontoLuminescentMaterialsandLuminescenceEnergyTransfer 348
13.2.1 PhotoexcitationofLuminescentMaterials 349
13.2.2 ReturntotheGroundState 351
13.3 ElectronicTransitionsandOpticalPropertiesofSpin-CrossoverComplexes 358
13.4 MaterialswithCombinedSpin-CrossoverandLuminescentFunctionalities 361
13.4.1 GeneralConsiderations 361
13.4.2 ExamplesofLuminescentSpin-CrossoverCompounds(Ligands,
Counterions) 362
13.4.3 LuminescentDoping 366
13.5 ConcludingRemarks 371
Acknowledgements 372
References 372
14 Nanoparticles,ThinFilmsandSurfacePatternsfromSpin-CrossoverMaterialsand
ElectricalSpinStateControl 375
PauloNunoMartinho,CyrilRajnakandMarioRuben
14.1 Introduction 375
14.2 NanoparticlesandNanocrystals 376
14.2.1 ReverseMicelle(Microemulsion)Technique 376
14.2.2 Sol-GelTechniques 386
14.3 ThinFilms 387
14.3.1 Langmuir–BlodgettDeposition 387
14.3.2 Surface-AssistedMolecularSelf-assembly 390
14.3.3 DiverseTechniques 390
Contents xi
14.4 SurfacePatterns 393
14.4.1 SurfacePatternsofSpin-Crossover 393
14.5 ElectricalSpinStateControl 396
14.6 Conclusion 399
References 400
15 UltrafastStudiesoftheLight-InducedSpinChangeinFe(II)-PolypyridineComplexes 405
MajedChergui
15.1 Introduction 405
15.2 PropertiesofFe(II)Complexes 406
15.2.1 ElectronicStructure 406
15.2.2 MolecularStructure 407
15.2.3 VibrationalModes 407
15.2.4 KineticsofGroundStateRecovery 408
15.3 FromtheSinglettotheQuintetState 408
15.3.1 DepartingfromtheMCLTManifold 409
15.3.2 ArrivalintotheHSState 412
15.3.3 VibrationalrelaxationoftheHSState 414
15.4 UltrafastX-RayStudies 415
15.5 SummaryandOutlook 417
Acknowledgements 419
References 420
16 Real-TimeObservationofSpin-TransitionsbyOpticalMicroscopy 425
Franc¸oisVarret,ChristianChong,AhmedSlimani,DamienGarrot,YannGarciaandAnilD.Naik
16.1 Introduction 425
16.2 ExperimentalAspects 426
16.2.1 SingleCrystals 426
16.2.2 TheSampleCell 426
16.2.3 Cryostat,Objective,Camera 427
16.2.4 SettingoftheCryostat 427
16.2.5 ObservationModes 428
16.3 SelectedInvestigations 429
16.3.1 TheInterplaybetweenStructureandSpinTransformations:
[Fe(bbtr) ](ClO ) 429
3 4 2
16.3.2 ColorimetricInvestigationof[Fe(ptz) ](BF ) 430
6 4 2
16.3.3 TheTransformationFrontin[Fe(btr) (NCS) ]·H OCrystals 433
2 2 2
16.3.4 TheEvolutionoftheFrontlinein[Fe(bbtr) ](ClO ) Crystals 436
3 4 2
16.3.5 AnExampleofaRobustCrystal:[Fe(btr) ](ClO ) 437
3 4 2
16.4 ConclusionsandProspects 439
Acknowledgements 439
References 440
17 TheoreticalPredictionofSpin-CrossoverattheMolecularLevel 443
RobertJ.Deeth,ChristopherM.HandleyandBenjaminJ.Houghton
17.1 Introduction 443
17.2 Beginnings:ValenceBondandLigandFieldTheories 443