Table Of ContentStructure and Bonding 164
Series Editor: D.M.P. Mingos
Song Gao Editor
Molecular
Nanomagnets
and Related
Phenomena
164
Structure and Bonding
SeriesEditor:
D.M.P.Mingos,Oxford,UnitedKingdom
EditorialBoard:
F.A.Armstrong,Oxford,UnitedKingdom
X.Duan,Beijing,China
L.H.Gade,Heidelberg,Germany
K.R.Poeppelmeier,Evanston,IL,USA
G.Parkin,NewYork,USA
M.Takano,Kyoto,Japan
Aims and Scope
The series Structure and Bonding publishes critical reviews on topics of research
concerned with chemical structure and bonding. The scope of the series spans the
entirePeriodicTableandaddressesstructureandbondingissuesassociatedwithallof
the elements. It also focuses attention on new and developing areas of modern
structural and theoretical chemistry such as nanostructures, molecular electronics,
designed molecular solids, surfaces, metal clusters and supramolecular structures.
Physicalandspectroscopictechniquesusedtodetermine,examineandmodelstruc-
turesfallwithinthepurviewofStructureandBondingtotheextentthatthefocusison
the scientific results obtained and not on specialist information concerning the
techniques themselves. Issues associated with the development of bonding models
and generalizations that illuminate the reactivity pathways and rates of chemical
processesarealsorelevant
Theindividualvolumesintheseriesarethematic.Thegoalofeachvolumeistogive
thereader,whetheratauniversityorinindustry,acomprehensiveoverviewofanarea
where new insights are emerging that are ofinterest toa larger scientific audience.
Thus each review within the volume criticallysurveysone aspect ofthattopic and
placesitwithinthecontextofthevolumeasawhole.Themostsignificantdevelop-
mentsofthelast5to10yearsshouldbepresentedusingselectedexamplestoillustrate
the principles discussed. A description of the physical basis of the experimental
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ifithasnotbeencoveredindetailelsewhere.Thecoverageneednotbeexhaustivein
data, but should rather be conceptual, concentrating on the new principles being
developed that will allow the reader, who is not a specialistinthe areacovered,to
understandthedatapresented.Discussionofpossiblefutureresearchdirectionsinthe
areaiswelcomed.
Reviewarticlesfortheindividualvolumesareinvitedbythevolumeeditors.
In references Structure and Bonding is abbreviated Struct Bond and is cited as a
journal.
Moreinformationaboutthisseriesat
http://www.springer.com/series/430
Song Gao
Editor
Molecular Nanomagnets
and Related Phenomena
With contributions by
(cid:1) (cid:1) (cid:1) (cid:1)
M. Affronte M.L. Baker S.J. Blundell L. Bogani
L.F. Chibotaru (cid:1) R. Cle´rac (cid:1) A. Cornia (cid:1) C. Coulon (cid:1)
(cid:1) (cid:1) (cid:1) (cid:1) (cid:1)
N. Domingo M. Evangelisti S. Gao A. Ghirri S. Hill
(cid:1) (cid:1) (cid:1) (cid:1) (cid:1)
S.-D. Jiang F. Luis M. Mannini C.J. Milios V. Pianet
(cid:1) (cid:1) (cid:1)
F. Troiani M. Urdampilleta R.E.P. Winpenny
B.-W. Wang
Editor
SongGao
Coll.ofChemistryandMolecularEng
PekingUniversity
Beijing
China
ISSN0081-5993 ISSN1616-8550 (electronic)
StructureandBonding
ISBN978-3-662-45722-1 ISBN978-3-662-45723-8 (eBook)
DOI10.1007/978-3-662-45723-8
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Preface
The discovery of single-molecule magnets (SMMs) at the beginning of the 1990s
openedanewinterdisciplinaryfieldinbetweenchemistry,physics,materials,and
nanoscience. The first SMM Mn12 cluster is a nanoscale molecule showing slow
magnetic relaxation and quantum tunneling of magnetization. Some molecular
nanowires with similar behaviors were found about 10 years later and named as
single-chain magnets (SCMs). In the following decade, a few single-ion magnets
(SIMs)werereported;theycanbeconsideredasanewfamilyofmolecularnano-
magnets(MNs).
In 2006, volume 122 of Structure and Bonding had been devoted to “Single-
MoleculeMagnetsandRelatedPhenomena,”editedbyRichardWinpenny.Thisis
a continued volume and extended to more wide and comprehensive topics in the
rapidgrowthfield.Someauthorsoflastvolumealsohavetheircontributionstothis
volume. This volume covers various molecular nanomagnets, from materials to
magnetismtodeviceandfrombasistomethodtoapplication.
Thisvolumeconsistsofninechapters:thefirstfivechaptersmainlyfocusonthe
different molecular nanomagnets, their synthesis, structures, intrinsic magnetic
properties,theoreticalandexperimentalmethods;thefollowedfourchaptersmain-
lyfocusonrelatedphenomenaandpotentialapplications.
The first chapter of this volume by Milios and Winpenny mainly focuses on
the development of cluster-based SMMs since 2005 and summarizes astonishing
number of beautiful new cluster-based SMMs, from 3d to 4d/5d, to 4f-elements.
Theclustersreportedhereinarecategorizedandcommentedintermsoftheirmetal
contentfromthesyntheticchemist’spointofview.
From 2003, SMMs have been extended from clusters to some mononuclear
lanthanide coordination compounds or organometallics. In the second chapter
Jiang, Wang, and Gao review four series of well-investigated lanthanide single-
ion magnets, theoretical and experimental investigation methods, especially the
advancedmethodsoftheangle-resolvedmagnetometrymeasurementonlanthanide
ions.TransitionmetalbasedSIMsarenotincluded.
v
vi Preface
Inthethirdchapter,thestaticanddynamicmagneticpropertiesofsingle-chain
magnets and related systems are reviewed by Coulon, Pianet, Urdampilleta, and
Clee´rac based on a theoretical point of view. Authors particularly focus on the
so-calledIsinglimit,fromsimpleregularchainofferromagneticallycoupledspins,
to more complicated structures including chains of antiferromagnetically coupled
magnetic sites. The section “from SCM to 3D ordered systems” provides a new
insightintothesinglechainmagnets.
The understanding of mechanisms of magnetic anisotropy in molecular nano-
magnets became a task of primary importance in the last decade. In the fourth
chapter,Chibotarudiscussesthephysicalreasons for magneticanisotropyandthe
mechanisms of its appearance in mononuclear and polynuclear metal complexes.
Differences in the manifestation of magnetic anisotropy between complexes with
weakandstrongspin-orbitcouplingareemphasized.
Following the theoretical chapter, four physicists Baker, Blundell, Domingo,
and Stephen Hill present a fairly comprehensive review of some of the primary
spectroscopicmethodsthathavecontributedtothecurrentunderstandingofmolec-
ularnanomagnets.Theseinclude:electronparamagneticresonance(EPR);optical
spectroscopy, including magnetic and X-ray magnetic circular dichroism
(MCD/XMCD); inelastic neutron scattering (INS); and muon spin rotation
(m+SR).Eachsectionprovidesabackgroundofthephysicsofthetechniquesbefore
launchingintosomewell-selectedexamples.
Inthesixthchapter,CorniaandManninipresentacriticaloverviewofthelatest
achievements in the deposition of SMMs as monolayers or submonolayers on
native or prefunctionalized surfaces. Special emphasis is placed on the selection
anddesignofmolecularstructuresthatwithstandsolution-orvapor-phaseproces-
singandmaintaintheirmagneticfunctionalityonasurface.
In the seventh chapter, Bogani reviews the experimental state of the art of
molecular spintronics using molecular magnet. After a brief introduction to the
fundamental concepts in the field, all possible approaches to fabricate molecular
spintronicdeviceshavebeensummarized.Healsoprovidesabriefdiscussionofthe
future directions and the considerable challenges that remain unexplored in the
field.
Another potential application of molecular nanomagnets is quantum computa-
tion. Ghirri, Troiani, and Affronte introduce basic concepts, stressing analogies
betweenthephysicsandthechemistryofmolecularnanomagnetsandthescienceof
computing.Theyreviewmainachievements,presentchallenges,andfocusontwo
emergingtopics:quantumsimulatorsandhybridsystemsmadebyresonantcavities
andmolecularnanomagnets.
Last chapter by Luis and Evangelisti review history, materials, and underlying
physics that form a background common to magnetic refrigeration and spin–
lattice relaxation. To illustrate how these subjects are profoundly interrelated
with each other, they describe studies performed on two gadolinium-based single
molecule magnets and their promising applications as low temperature magnetic
refrigerants.
Preface vii
Lastbutnotleast,Iamgreatlyindebtedtoallauthorswho havecontributedto
theseimportantandexcitingtopicsandIhopethatthereaderswillfindthisvolume
useful,stimulating,andinspirationaltotheirresearch.Ialsogreatlyappreciatethe
helpofJuneTang,ChemistryEditorofSpringer,inorganizingthisvolume.
Beijing,China SongGao
October2014
ThiSisaFMBlankPage
Contents
Cluster-BasedSingle-MoleculeMagnets....................................... 1
ConstantinosJ.MiliosandRichardE.P.Winpenny
AdvancesinLanthanideSingle-IonMagnets ............................... 111
Shang-DaJiang,Bing-WuWang,andSongGao
Single-ChainMagnetsandRelatedSystems ................................ 143
ClaudeCoulon,VivienPianet,MatiasUrdampilleta,andRodolpheCle´rac
TheoreticalUnderstandingofAnisotropyinMolecular
Nanomagnets................................................................... 185
LiviuF.Chibotaru
SpectroscopyMethodsforMolecularNanomagnets........................ 231
MichaelL.Baker,StephenJ.Blundell,NeusDomingo,andStephenHill
Single-MoleculeMagnetsonSurfaces ....................................... 293
AndreaCorniaandMatteoMannini
ExperimentsonMolecularMagnetsforMolecularSpintronics........... 331
LapoBogani
QuantumComputationwithMolecularNanomagnets:Achievements,
Challenges,andNewTrends ................................................. 383
AlbertoGhirri,FilippoTroiani,andMarcoAffronte
MagneticRefrigerationandSpin–LatticeRelaxationin
Gadolinium-BasedMolecularNanomagnets ................................ 431
FernandoLuisandMarcoEvangelisti
Index............................................................................ 461
ix
