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Structure 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 techniquesthathavebeenusedtoprovidetheprimarydatamayalsobeappropriate, 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 LibraryofCongressControlNumber:2015933274 SpringerHeidelbergNewYorkDordrechtLondon #Springer-VerlagBerlinHeidelberg2015 Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpart of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilarmethodologynowknownorhereafterdeveloped. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publicationdoesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexempt fromtherelevantprotectivelawsandregulationsandthereforefreeforgeneraluse. Thepublisher,theauthorsandtheeditorsaresafetoassumethattheadviceandinformationinthis book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, express or implied, with respect to the material contained hereinorforanyerrorsoromissionsthatmayhavebeenmade. Printedonacid-freepaper Springer-Verlag GmbH Berlin Heidelberg is part of Springer Science+Business Media (www.springer.com) 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 nanomagnets 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