Lanthanides and Actinides in Molecular Magnetism

358 Pages·2015·5.12 MB·English

by  Richard A. Layfield and Muralee Murugesu

Editedby
RichardA.LayfieldandMuraleeMurugesu
LanthanidesandActinidesinMolecular
Magnetism
RelatedTitles
deBettencourt-Dias,A.(ed.) Hilzinger,R.,Rodewald,W.
LuminescenceofLanthanide MagneticMaterials
IonsinCoordination Fundamentals,Products,Properties,
Applications
Compoundsand
Nanomaterials 2013
PrintISBN:978-3-895-78352-4
2014
PrintISBN:978-1-119-95083-7
(Alsoavailableinavarietyofelectronicformats)
Gatteschi,D.,Benelli,C.
IntroductiontoMolecular
Magnetism
FromTransitionMetalstoLanthanides
2015
PrintISBN:978-3-527-33540-4
(Alsoavailableinavarietyofelectronicformats)
Editedby
RichardA.LayfieldandMuraleeMurugesu
Lanthanides and Actinides in Molecular
Magnetism
TheEditors AllbookspublishedbyWiley-VCHare
carefullyproduced.Nevertheless,authors,
Dr.RichardA.Layfield editors,andpublisherdonotwarrantthe
TheUniversityofManchester informationcontainedinthesebooks,
SchoolofChemistry includingthisbook,tobefreeoferrors.
OxfordRoad Readersareadvisedtokeepinmindthat
M139PLManchester statements,data,illustrations,procedural
UnitedKingdom detailsorotheritemsmayinadvertently
beinaccurate.
Prof.Dr.MuraleeMurugesu
UniversityofOttawa LibraryofCongressCardNo.:appliedfor
DepartmentofChemistry/D’IorioHall
MarieCurie10 BritishLibraryCataloguing-in-Publication
ONK1N6NNK Data
Canada Acataloguerecordforthisbookis
availablefromtheBritishLibrary.
Cover
Periodictable:iStockphoto©Tomacco Bibliographicinformationpublishedbythe
Magnet:iStockphoto©jgroup DeutscheNationalbibliothek
TheDeutscheNationalbibliothek
liststhispublicationintheDeutsche
Nationalbibliografie;detailed
bibliographicdataareavailableonthe
Internetat<http://dnb.d-nb.de>.
©2015Wiley-VCHVerlag&Co.KGaA,
Boschstr.12,69469Weinheim,Germany
Allrightsreserved(includingthoseof
translationintootherlanguages).Nopart
ofthisbookmaybereproducedinany
form–byphotoprinting,microfilm,
oranyothermeans–nortransmitted
ortranslatedintoamachinelanguage
withoutwrittenpermissionfromthe
publishers.Registerednames,trademarks,
etc.usedinthisbook,evenwhennot
specificallymarkedassuch,arenottobe
consideredunprotectedbylaw.
PrintISBN:978-3-527-33526-8
ePDFISBN:978-3-527-67350-6
ePubISBN:978-3-527-67349-0
MobiISBN:978-3-527-67348-3
oBookISBN:978-3-527-67347-6
Typesetting LaserwordsPrivateLimited,
Chennai,India
PrintingandBinding MarkonoPrint
MediaPteLtd,Singapore
Printedonacid-freepaper
V
Contents
Preface XIII
ListofContributors XV
1 ElectronicStructureandMagneticPropertiesofLanthanideMolecular
Complexes 1
LorenzoSoraceandDanteGatteschi
1.1 Introduction 1
1.2 FreeIonElectronicStructure 3
1.2.1 FreeIonMagnetism 6
1.3 ElectronicStructureofLanthanideIonsinaLigandField 7
1.3.1 Stevens’Formalism 9
1.3.2 Wybourne’sFormalism 9
1.3.3 Standardization 13
1.3.4 CalculationofCrystalFieldParameters 13
1.4 MagneticPropertiesofIsolatedLanthanideIons 16
1.4.1 EffectofaMagneticField 16
1.4.2 EPRSpectroscopyofLanthanideComplexes 17
1.5 ExchangeCouplinginSystemsContainingOrbitallyDegenerate
Lanthanides 21
Acknowledgements 23
References 23
2 MononuclearLanthanideComplexes:UseoftheCrystalFieldTheory
toDesignSingle-IonMagnetsandSpinQubits 27
JuanM.Clemente-Juan,EugenioCoronado,and
AlejandroGaita-Ariño
2.1 Introduction 27
2.2 ModellingtheMagneticPropertiesofLanthanideSingle-Ion
Magnets:TheUseoftheCrystalFieldModel 29
2.2.1 TheoreticalBackground 29
VI Contents
2.2.2 HowtoDeterminetheCrystal-FieldParameters:1.TheIshikawa
Approach 30
2.2.3 HowtoDeterminetheCrystal-FieldParameters:2.ThePointCharge
ElectrostaticModel 34
2.2.4 HowtoDeterminetheCrystal-FieldParameters:3.TheEffective
PointChargeModel 36
2.3 Magneto-StructuralCorrelationsforSomeTypicalSymmetries 40
2.4 ImpactofLanthanideComplexesinQuantumComputing 44
2.4.1 QuantumComputingParadigmsandDesignCriteria 45
2.4.2 CombiningPhysicalQubitImplementationswithLanthanide
Complexes 48
2.4.3 MolecularSpinQubits 50
2.5 Conclusions 53
Acknowledgements 54
References 55
3 PolynuclearLanthanideSingleMoleculeMagnets 61
JinkuiTangandPengZhang
3.1 Introduction 61
3.2 SyntheticStrategies 62
3.2.1 Dy TrianglesandTheirDerivatives 64
3
3.2.1.1 SeminalDy Triangle 64
3
3.2.1.2 OtherTriangularDy Systems 65
3
3.2.1.3 TheCouplingofDy Triangles 68
3
3.2.2 LinearPolynuclearLanthanideComplexesShowingRobustSMM
Behaviour 71
3.2.2.1 LinearDy SMMs 72
3
3.2.2.2 LinearDy SMMs 73
4
3.2.3 PlanarDy SMMs 75
4
3.2.4 Dy SMMsHavingMultipleμ -O(n>4)Bridges 78
n n
3.2.4.1 TheDy GridsFixedbyμ -OAtom 78
4 4
3.2.4.2 TheDy TetrahedronFixedbyμ -OAtom 80
4 4
3.2.4.3 TheDy PyramidFixedbyμ -OAtom 80
5 5
3.2.5 Hydrazone-BasedLanthanideSMMs 82
3.2.5.1 TheAssemblyofDy TriangularPrismwithDy Units 83
6 2
3.2.5.2 ADy MolecularClusterPair(Dy ) 84
3 6
3.2.6 TheOrganometallicSynthesis—ANewApproach 85
3.3 Conclusion 86
References 86
4 LanthanidesinExtendedMolecularNetworks 89
RobertaSessoliandKevinBernot
4.1 Introduction 89
Contents VII
4.2 ExtendedNetworksBasedonGd3+ 91
4.2.1 Metal-OrganicFrameworks 91
4.2.1.1 Magneto-CaloricEffect 91
4.2.1.2 SlowMagneticRelaxationandPhononBottleneckEffects 94
4.2.2 MagneticChains 96
4.2.2.1 MagneticInteractionsInvolvingGd3+Ions 96
4.2.2.2 Gadolinium-RadicalChains 96
4.3 ExtendedNetworksBasedonAnisotropicIons 101
4.3.1 SCMinaNutshell 101
4.3.2 AnOverviewofMonodimensionalLanthanideChainsBasedon
AnisotropicIons 104
4.3.2.1 ChainsBasedon4fIons 104
4.3.2.2 ChainsBasedon3d–4fIons 106
4.3.2.3 ChainsBasedonRadicalsand4fIons 111
4.3.3 TheKeyPointofNoncollinearityofMagneticAnisotropy 112
4.4 Conclusions 119
References 119
5 ExperimentalAspectsofLanthanideSingle-MoleculeMagnet
Physics 125
KasperS.Pedersen,DanielN.Woodruff,JesperBendix,andRodolpheClérac
5.1 Introduction 125
5.2 ManifestationofSingle-MoleculeMagnetBehaviour 127
5.2.1 MagnetizationandacSusceptibilityMeasurements 127
5.2.2 NMRSpectroscopy 132
5.2.3 MuonSpinRotation 133
5.3 QuantifyingtheMagneticAnisotropy 135
5.4 SplittingoftheGroundMultiplet 139
5.4.1 MagneticResonanceSpectroscopies 139
5.4.2 LuminescenceSpectroscopy 140
5.4.3 InelasticNeutronScattering 141
5.5 ObservationoftheSignaturesofExchangeCoupling 146
5.5.1 ChemicalSubstitution 146
5.5.2 X-RayMagneticCircularDichroism 147
5.6 ConcludingRemarksandPerspectives 149
References 150
6 ComputationalModellingoftheMagneticPropertiesofLanthanide
Compounds 153
LiviuUngurandLiviuF.Chibotaru
6.1 Introduction 153
6.2 AbInitioDescriptionofLanthanidesanditsRelationtoOther
Methods 153
VIII Contents
6.2.1 AbInitioApproachfortheElectronicStructureofLanthanides 155
6.2.1.1 AccountingforStaticElectronCorrelationwithinCASSCF 155
6.2.1.2 AccountingforDynamicalElectronCorrelation:AnImportantStep
TowardsAccuratePredictions 155
6.2.1.3 AccountingforRelativisticEffectswithintheDouglas–Kroll–Hess
Theory 156
6.2.1.4 Spin–OrbitMultipletsofFreeLanthanideIons:Relativistic
CASSCF/RASSIMethodinWork 157
6.2.2 AbInitioVersusTwo-ComponentDFT 159
6.2.3 AbInitioVersusPhenomenologicalCrystalFieldTheoryfor
Lanthanides 159
6.3 AbInitioCalculationofAnisotropicMagneticProperties
ofMononuclearComplexes 160
6.3.1 ImplementationofAbInitioMethodology:SINGLE_ANISO
Program 161
6.3.2 Temperature-DependentMagneticSusceptibilityand
Field-DependentMagnetization 163
6.3.3 MagneticAnisotropyinLow-LyingDoublets 164
6.3.4 AbInitioCrystalField 166
6.4 AbInitioCalculationofAnisotropicMagneticProperties
ofPolynuclearComplexes 169
6.4.1 Two-StepApproachfortheCalculationofElectronicStructure
ofPolynuclearLanthanideComplexes 170
6.4.2 KeyRulesforClusterFragmentation 170
6.4.3 ImplementationofAbInitioMethodology:POLY_ANISO
Program 171
6.4.4 NoncollinearMagneticStructureofLn Complexes 172
n
6.4.5 MixedLanthanide-TransitionMetalCompounds 176
6.4.6 Lanthanide-ContainingMagneticChains 178
6.5 Conclusions 180
References 181
7 LanthanideComplexesasRealizationsofQubitsandQugates
forQuantumComputing 185
GuillemAromı́,FernandoLuis,andOlivierRoubeau
7.1 IntroductiontoQuantumComputation 185
7.1.1 GeneralIntroduction 185
7.1.2 DefinitionofQubits,Qugates,TimescalesandEssential
Requirements 186
7.1.3 CurrentProposalsfortheQCHardware 189
7.1.3.1 TrappedIons 189
7.1.3.2 NuclearSpins 190
7.1.3.3 SuperconductingQubits 191
Contents IX
7.1.3.4 SpinQubits 191
7.1.3.5 Photons 191
7.1.3.6 HybridProposalsandQuantumCircuits 192
7.2 QuantumComputingwithElectronSpinQubits 192
7.2.1 ElectronicSpinsinSemiconductors:QDsandDopants 192
7.2.1.1 QuantumDots 193
7.2.1.2 DopantsandDefects 193
7.2.2 ElectronicSpinsinMolecules:OrganicRadicalsandTransition
MetalComplexes 194
7.2.2.1 OrganicRadicals 194
7.2.2.2 TransitionMetalComplexes 195
7.3 SingleLanthanideIonsasSpinQubits 197
7.3.1 QuantumCoherenceofLanthanideIonsDopedintoCrystalline
Solids 198
7.3.2 ControloftheMagneticAnisotropyofLanthanideIons:Chemical
DesignofSpinQubits 199
7.3.2.1 MononuclearSingleMoleculeMagnets 199
7.3.2.2 Gadolinium(III)POMsasSpinQubits 200
7.3.2.3 MononuclearSMMsofLn(III)IonswithNonzeroOrbital
Moment 202
7.4 LanthanideMoleculesasPrototypesofTwo-QubitQuantum
Gates 204
7.4.1 AFamilyofAsymmetric[Ln ]ComplexeswithWeakMagnetic
2
Coupling 204
7.4.2 Heterometallic[LnLn′]Complexes:AFabricofChemical
AsymmetryandIndividualQubits 208
7.4.3 EvaluatingQubitProperties 209
7.4.4 WeakCoupling 211
7.4.5 AsymmetryandEnergyDiagrams 212
7.4.6 DecoherenceoftheMolecularQuantumProcessorPrototypes 215
7.5 ConclusionsandOutlook 215
References 216
8 Bis(phthalocyaninato)Lanthanide(III)Complexes–fromMolecular
MagnetismtoSpintronicDevices 223
YanhuaLan,SvetlanaKlyatskaya,andMarioRuben
8.1 Introduction 223
8.1.1 MolecularMagnetism 223
8.1.2 MultinuclearVersusMononuclear:d-Versusf-MetalIons 224
8.1.3 MolecularVersusOrganicSpintronics 227
8.2 SynthesisandStructureofLnPc Complexes 229
2
8.2.1 SynthesisofBis(phthalocyaninato)Lanthanide(III)Complexes 229
X Contents
8.2.2 SynthesisofHeterolepticLanthanide(III)ComplexesContaining
Porphyrin-BasedLigands 235
8.2.3 OxidationStatesofBis(phthalocyaninato)Lanthanide(III)
Complexes 239
8.2.4 RotationAnglesandSkewAnglesinLnPc inRelationtothe
2
LanthanideContraction 243
8.3 BulkMagnetismofLnPc Complexes 246
2
8.3.1 MagnetismofBis(phthalocyaninato)Lanthanide(III)
Complexes 246
8.3.2 ThreeSpinSystemsin[TbPc ]0Single-IonMolecularMagnets
2
(SIMMs) 246
8.3.2.1 TheOrganicRadical(S) 246
8.3.2.2 TheElectronicSpin(J) 248
8.3.2.3 TheNuclearSpin(I) 249
8.3.3 FurtherSIMsofLnPc withLn=Tb,DyandHo 249
2
8.3.4 InternalKondoinLnPc ComplexeswithLn=Ce,Yb 255
2
8.3.5 StableOrganicRadicalsS=1∕2inLnPc withLn=Y,Lu 257
2
8.3.6 ASpecialCase:Half-Fillingofthef-OrbitalsinGdPc andits
2
Consequences 258
8.4 SurfaceMagnetismofLnPc Complexes 259
2
8.4.1 Depositionof[TbPc ]0SIMMsonNonmagnetic
2
Substrates 261
8.4.1.1 HighlyOrientedPyroliticGraphite 261
8.4.1.2 Au(111) 262
8.4.1.3 Cu(111) 263
8.4.1.4 Cu(100) 265
8.4.2 Depositionof[TbPc ]0SIMsonMagneticSubstrates 267
2
8.4.2.1 NickelThinFilms 267
8.4.2.2 CobaltThinFilms 269
8.4.2.3 LSMO 269
8.4.2.4 ManganeseandCobaltOxideLayers 269
8.4.2.5 SpinPolarizedScanningTunnellingMicroscopy(SP-STM)
onCo/Ir(111) 270
8.5 MolecularSpintronicDevicesontheBase
of[TbPc ]0SIMs 272
2
8.5.1 GrapheneTransistor 274
8.5.2 SupramolecularSpinValve 276
8.5.3 MolecularSpinResonator 278
8.5.4 MolecularSpinTransistor 280
8.6 ConclusionandOutlook 281
Abbreviations 283
References 284