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Keith Murray Editor Single Molecule Toroics Synthetic Strategies, Theory and Applications Single Molecule Toroics Keith Murray Editor Single Molecule Toroics Synthetic Strategies, Theory and Applications Editor KeithMurray SchoolofChemistry MonashUniversity Clayton,VIC,Australia ThisworkwassupportedbytheAustralianResearchCouncil ISBN978-3-031-11708-4 ISBN978-3-031-11709-1 (eBook) https://doi.org/10.1007/978-3-031-11709-1 ©TheEditor(s)(ifapplicable)andTheAuthor(s),underexclusivelicensetoSpringerNatureSwitzerland AG2022 Thisworkissubjecttocopyright.AllrightsaresolelyandexclusivelylicensedbythePublisher,whether thewhole orpart ofthematerial isconcerned, specifically therights oftranslation, reprinting, reuse ofillustrations, recitation, broadcasting, reproductiononmicrofilmsorinanyotherphysicalway,and transmissionorinformationstorageandretrieval,electronicadaptation,computersoftware,orbysimilar ordissimilarmethodologynowknownorhereafterdeveloped. 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ThisSpringerimprintispublishedbytheregisteredcompanySpringerNatureSwitzerlandAG Theregisteredcompanyaddressis:Gewerbestrasse11,6330Cham,Switzerland Preface Theaimofthepresentbookistoshowtheexcitinggrowthinsinglemoleculetoroics (SMTs)withemphasisonsynthesis,structure,magnetism,EPRandtheory.Perusal ofrecentreviewsshowsthatcycliclanthanidespecies(mainlyDyIII)predominate, viz. triangles, squares, hexagons and multiple triangles, with a few non-cyclic examples recently discovered. Large heterometallic 3d/4f cluster SMTs are also emerging(seeChaps.2,3,and4). In Chap. 2, Stuart Langley, Alessandro Soncini, Kieran Hymas, Kuduva Vig- nesh, Gopalan Rajaraman and Keith Murray describe the synthesis, structures, magnetism,EPRandtheoryofmixedd-f-blockandp-f-blockSMTs,withemphasis on ‘double triangle’ {MLn } heptanuclears, in which variations have been made 6 in the linking MIII ion (Cr, Mn, Fe, Co, Al, Ga), the f-ion (Dy, Tb, Ho for Ln = − − Dy) and the counteranion (NO , Cl ). One of the highlights of this work has 3 beenthedevelopmentoftheorythathasallowedthesimulationofthemicroSquid hystereticloops,measuredat0.03K,byWolfgangWernsdorfer,withcharacteristic ‘stepped’ shapes that were first noted in the early Dy work. This work has led 3 to the discovery and confirmation of several significant trends in the energetic, structural and magnetic properties of these materials. These trends are the first toroido-structuralcorrelationstobereportedandconstituteanewtypeofmagneto- structuralcorrelation. Xiao-LeiLiandJinkuiTangdescribedesignandsyntheticstrategiesinChap.3. TheyshowhowO-donor,N-donorandO,Ndonorchelatingligandsleadtodesirable SMTs.TangandAnniePowellworkedtogetheronthefirstDy SMTtriangles.We 3 seeherehowthedesignstrategiescompareandhowtheyhavechanged. In Chap. 4, Hao-Lan Zhang, Yuan-Qi Zhai and Yan-Zhen Zheng rationalise room-temperature SMT behaviour via FeIII-DyIII exchange coupling in a FeIII DyIII cyclic cluster. They begin their chapter with a survey of dysprosium 8 8 SMTsandd-f-blockheterometallicSMTs. Spin-electric coupling, magnetoelectricity, and quantum dynamics of toroidal moments in lanthanide based single molecule toroics are described by Dmitry Plokhov,AlexanderPyatakov,AlexanderPopovandAnatolyK.ZvezdininChap.5. v vi Preface Detailedtheoryispresentedandtheimportancetomolecularspintronicsisempha- sisedaswellasthefutureuseofSMTsasqubitsinquantumcomputing. Turning again to theory, applicable to SMTs, Alessandro Soncini and Kieran Hymas, in Chap. 6, go beyond the semi-classical Ising approximation in their investigationintoquantumsingle-moleculetoroics.UtilisingaunifyingHeisenberg exchange model, they describe quantum toroidicity in single-molecule toroics with ring-like exchange connectivities in both the strong and weak magnetic anisotropyregimes.Byaccountingforquantumspinfluctuationsofthemagnetically anisotropicions,tunnellingstatesofthetoroidalmomentcanbenaturallyrealised, settingthestageforquantumcomputationbasedonmoleculartoroidalqubits. Clayton,VIC,Australia KeithMurray May2022 Acknowledgements The authors wish to thank AngelikiAthanasopoulou,Karthika Menon and Rekha KumarJayakumarofSpringerNaturefortheirefficienthelpandpatience. vii Contents 1 IntroductiontoSingle-MoleculeToroics .................................. 1 Keith S. Murray, Kuduva R. Vignesh, Kieran Hymas, andAlessandroSoncini 2 Mixedd-f BlockSingle-MoleculeToroics................................. 15 Keith S. Murray, Stuart K. Langley, Kuduva R. Vignesh, GopalanRajaraman,KieranHymas,andAlessandroSoncini 3 Single-MoleculeToroics:DesignandSyntheticStrategies.............. 67 Xiao-LeiLiandJinkuiTang 4 Rationalizationof Room-TemperatureSingle-Molecule ToroicsviaExchangeCoupling............................................. 107 Hao-LanZhang,Yuan-QiZhai,andYan-ZhenZheng 5 Spin-ElectricCoupling,Magnetoelectricity,andQuantum DynamicsofToroidalMomentinLanthanide-BasedSingle MoleculeToroics ............................................................. 133 Dmitry Plokhov, Alexander Pyatakov, Alexander Popov, andAnatolyK.Zvezdin 6 QuantumToroidicityinSingle-MoleculeToroics:AUnifying ModelBasedonHeisenbergSpinRings................................... 189 KieranHymasandAlessandroSoncini Index............................................................................... 233 ix Editor and Contributors AbouttheEditor KeithS.Murray gainedhisPhDattheUniversityofManchester,in1966,under David Machin’s supervision. He joined Monash University in Clayton, Australia, as a senior teaching fellow, his research dealing with the syntheses, spectral and magneticpropertiesoftransitionmetalcomplexes.Hiswholeacademiccareerhas beenatMonashUniversity,climbingtherankstoafullprofessorship.Presently,he is Emeritus Professor of Chemistry. In recent years, his research has focussed on molecularmagneticmaterialssuchassinglemoleculemagnetsandsingle-molecule toroics. The latter topic, involving mixed d-f-block compounds, formed the basis ofhisOlivierKahnMemorialLecturetotheInternationalConferenceonMolecule BasedMagnets,Manchester,2020. SchoolofChemistry,Building23,MonashUniversity,Clayton,Victoria,Australia Contributors KieranHymas SchoolofChemistry,UniversityofMelbourne,Parkville,Victoria, Australia Stuart K. Langley The Departmentof Natural Sciences, Chemistry, Manchester MetropolitanUniversity,Manchester,UK Xiao-LeiLi StateKeyLaboratoryofRareEarthResourceUtilization,Changchun InstituteofAppliedChemistry,ChineseAcademyofSciences,Changchun,People’s RepublicofChina KeithS.Murray SchoolofChemistry,Building23,MonashUniversity,Clayton, Victoria,Australia xi xii EditorandContributors DmitryI. Plokhov ProkhorovGeneralPhysicsInstituteofthe RussianAcademy ofSciences,Moscow,Russia PeoplesFriendshipUniversityofRussia(RUDNUniversity),Moscow,Russia Alexander I. Popov National Research University of Electronic Technology (MIET),Moscow,Russia Alexander P. Pyatakov Faculty of Physics, M. V. Lomonosov Moscow State University,Moscow,Russia Gopalan Rajaraman Department of Chemistry, Indian Institute of Technology Bombay,Mumbai,India Alessandro Soncini Department of Chemical Sciences, University of Padova, Padova,Italy JinkuiTang StateKeyLaboratoryofRareEarthResourceUtilization,Changchun InstituteofAppliedChemistry,ChineseAcademyofSciences,Changchun,People’s RepublicofChina SchoolofAppliedChemistryandEngineering,UniversityofScienceandTechnol- ogyofChina,Hefei,People’sRepublicofChina Kuduva R. Vignesh Department of Chemistry, Indian Institute of Technology Bombay,Mumbai,India Yuan-QiZhai FrontierInstituteofScienceandTechnology(FIST),Xi’anJiaotong UniversityShenzhenResearchSchool,StateKeyLaboratoryforMechanicalBehav- iorofMaterials,MOEKeyLaboratoryforNonequilibriumSynthesisofCondensed Matter, Xi’an Key Laboratory of Sustainable Energy and Materials Chemistry, School of Chemistry and School of Physics, Xi’an Jiaotong University, Shaanxi, China Hao-LanZhang FrontierInstituteofScienceandTechnology(FIST),Xi’anJiao- tong UniversityShenzhenResearch School,State Key Laboratoryfor Mechanical Behavior of Materials, MOE Key Laboratory for Nonequilibrium Synthesis of Condensed Matter, Xi’an Key Laboratory of Sustainable Energy and Materials Chemistry,SchoolofChemistryandSchoolofPhysics,Xi’anJiaotongUniversity, Shaanxi,China Yan-Zhen Zheng Frontier Institute of Science and Technology (FIST), Xi’an JiaotongUniversityShenzhenResearchSchool,StateKeyLaboratoryforMechan- ical Behavior of Materials, MOE Key Laboratory for Nonequilibrium Synthesis of Condensed Matter, Xi’an Key Laboratoryof Sustainable Energyand Materials Chemistry,SchoolofChemistryandSchoolofPhysics,Xi’anJiaotongUniversity, Shaanxi,China AnatolyK.Zvezdin ProkhorovGeneralPhysicsInstituteoftheRussianAcademy ofSciences,Moscow,Russia RussianQuantumCenter,Moscow,Russia P.N.LebedevPhysicalInstituteofRussianAcademyofSciences,Moscow,Russia NationalResearchUniversityHigherSchoolofEconomics,Moscow,Russia