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pubs.acs.org/JPCCArticleEnantioselectiveEffectsintheElectricalExcitationofAmineSingle-MoleculeRotorsTedrosA.Balema,YilangLiu,NatalieA.Wasio,AmandaM.Larson,DipnaA.Patel,PrashantDeshlahra,*andE.CharlesH.Sykes*CiteThis:J.Phys.Chem.C2021,125,3584−3589ReadOnlineACCESSMetrics&MoreArticleRecommendations*sıSupportingInformationABSTRACT:Thispaperdescribesasingle-moleculestudyofN-methylbutylaminemolecularrotorssupportedonaCu(111)surface.Itisfirstdemonstratedthatthechiralityoftheindividualrotatingmoleculescanbedirectlydeterminedbyscanningtunnelingmicroscopy(STM)imagingandunderstoodwithdensityfunctionaltheory(DFT)simulations.TunnelingelectronsfromtheSTMtiparethenutilizedtoexcitevibrationalmodesofthemoleculethatdrivestherotationalmotion.ExperimentalactionspectrawereusedtodemonstratethattheelectricallyinducedrotationalmotionofN-methylbutylamineoccursabove360meV,whichcoincideswithC−Hstretchingvibrationalmodes.Themeasure-mentsalsorevealthat,abovethis360meVthreshold,theexcitationoccursviaaone-electronprocess.DFTcalculationsindicatedthattherotationbarrierisoveranorderofmagnitudesmaller,meaningthattherotorisexcitedviahigh-energyvibrationalmodesthatthencoupletothelowenergyrotationalmode.Furthermore,byadjustingtheelectronflux,individualrotationalmotionsbetweenthesixdifferentstableorientationsofthemoleculeontheCu(111)surfaceweremonitoredinrealtime.Itwasfoundthat,formostSTMtipsusedtoelectricallyexcitetherotors,therotationofoneenantiomerisfasterthantheother.ThisconfirmsanearlierreportthatSTMtipscanthemselvesbechiralandillustratesthefactthatdiastereomerismarisingfromachiralSTMtipinteractingwithachiralmoleculecanleadtosignificantphysicaldifferencesintherotationratesofRversusSmolecularrotors.Thisresulthasramificationsforinterpretingthedatafromexperimentswherenanoscaleelectricalcontactstochiralmoleculesaremadeindeviceslikebreakjunctionsandscanningprobeexperiments.■INTRODUCTIONthecurrentwork,combiningSTManddensityfunctionaltheory(DFT)calculationshasledtoadeeperunderstandingMolecularrotors,motors,andmachinesareofcurrentinterest,27−31,35,36ofthioether-basedsingle-moleculerotorsandmotors.andtherecentliteraturecontainsmanyreportsoforganicSpecifically,electricallyinduceddirectionalmotionisonlyDownloadedviaUNIVOFPRINCEEDWARDISLANDonMay16,2021at06:14:04(UTC).molecularstructuresandtheirfunctionalityinarangeofSeehttps://pubs.acs.org/sharingguidelinesforoptionsonhowtolegitimatelysharepublishedarticles.chemically,thermally,orphoton-drivenprocesses.1−10Con-possiblewhentheadsorbedrotorischiralviaactivationofvibrationalmodesbytunnelingelectronsasopposedtosideringthatmolecularmachinesfoundinnatureoperateat11−21thermallyactivatedrotorsinwhichsecondlawthermody-interfaces,itisimportanttostudysurface-boundsystems.namicsdictatesthattheymustexhibitarandommo-However,factorssuchasfriction,thermalfluctuations,27−31,35,37tion.intramolecularbonding,andstericeffectshaveimposedThispaperdescribesasingle-moleculestudyofthevariouschallengesinunderstandingmanysurfacemolecular11,22rotationalmotionofchiralN-methylbutylaminerotorsmachines.Toaddressthesegapsinunderstanding,supportedonaCu(111)surface.Comparingtherelativescanningtunnelingmicroscopy(STM)offerstheuniquerotationalratesofthechiralN-methylbutylaminemolecularabilitytomakesingle-moleculemeasurementsofmolecularrotorsinducedbyinelastictunnelingelectrons,itwasobservedrotationonsurfacesandtointerrogatethedetailsofelectron-23−31inducedmolecularmotionatthenanoscale.Thankstothisapproach,therehavebeenimportantbreakthroughsinReceived:December1,2020studyingmolecularmachinessuchaselectricallydrivenRevised:January22,2021nanocars,32synchronizedmolecularmotornetworks,33andPublished:February5,202127,34single-moleculemotors.Whilestillfarfromapplication,molecularrotorsofferanidealtestbedfortheinvestigationofhowamolecularstructureaffectsdynamicalmotion.Relatedto©2021AmericanChemicalSocietyhttps://dx.doi.org/10.1021/acs.jpcc.0c107673584J.Phys.Chem.C2021,125,3584−3589
1TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticlethattherewasastrongenantioselectivecouplingbetweentheSTMtipandtheadsorbedchiralmoleculeleadingtolargedifferencesintheelectricallyexcitedrotationratesinRandSmolecularrotors.■EXPERIMENTALMETHODSLow-temperature(STM)LT-STMwasoperatedwithabasepressureof<1×10−11mbar.N-MethylbutylaminewasacquiredfromSigmaAldrichat95%purityandfurtherpurifiedbydegassingwithmultiplefreeze/pump/thawcycles.N-Methylbutylaminewasthenvapor-depositedontoaCu(111)sampleheldat5Kusingacollimatedmoleculardoserattachedtoaprecisionleakvalve.Annealsinthe80−120KrangewereperformedtoequilibratethemoleculesbyremovingthesamplefromthecryogenicallycooledstageofSTMandplacingitintoasampleholderheldatroomFigure1.(A)Schematicofsurface-adsorbedN-methylbutylamineontemperatureinanultrahighvacuum(UHV)chamberforaCu(111).TherotationalbehavioroftheaminerotoraroundtheN−Cu“axel”ishighlightedwithabluearrow.(B)Large-scale5KSTMpredeterminedtimeperiod.Thecrystalwasthencooledbackimageofsurface-adsorbedN-methylbutylamineonCu(111).Theto5KbyputtingitbackintotheSTMstageforhigh-greencirclesarerepresentativeexamplesoftheisolatedrotorresolutionimagingandspectracollection.EtchedWSTMtipsmoleculesusedinthestudy.Imagingconditions:10mV,90pA.wereusedinthisstudy.Scalebar:5nm.High-resolutionSTMimagesofaccompanyingtop-viewmodelsofthe(C)RenantiomerofanN-methylbutylamine■COMPUTATIONALDETAILSmoleculeadsorbedonCu(111)andthe(D)SenantiomerofanN-methylbutylaminemoleculeadsorbedonCu(111).Imagingcon-Periodicdensityfunctionaltheory(DFT)calculationswereditions:(C,D)20mV,200pA.Scalebars:0.5nm.performedwithintheViennaabinitiosimulationpackage(VASP)usingthePerdew−Burke−Ernzerhof(PBE)exchangetrateshowthemoleculecanrotatearoundtheN−Cubondcorrelationfunctionalbasedongeneralizedgradientapprox-38−41thatformstheaxelofthemolecularrotor.Figure1Bshowsaimation(GGA).Plane-wavebasissetsusedtoapprox-typicallargerSTMimagewithbothisolatedsinglemoleculesimatewavefunctionsofvalenceelectronswereexpandedtoaandsmallclusterspresent.Forthepurposeofthisstudyon400eVkineticenergycutoff.Theinteractionsofvalencesingle-moleculerotors,onlyisolatedmoleculesthatwereelectronswithatomcoresweredescribedbytheprojector-42severalnanometersfromanyneighboringmoleculeswereaugmentedwave(PAW)method.Electronicstructureswereexamined.Inthehigh-resolutionimagesinFigure1C,D,oneconvergedself-consistentlytoenergydifferenceslessthan1×−8canseefromtheindividualrotatingmoleculesthattheyare10eVbetweensuccessivesteps.Allsurfaceandbulkmetalmirrorimagesofoneanotherandhencechiral.Thiscalculationswereperformedwithoutspinpolarization.observationindicatesthat,whileenantiomersofN-methyl-TheCu(111)surfacewasrepresentedusingafour-layer4butylamineundergofastinterconversioninthegasphase,onCu×4CusupercellwithaboutsixlayersofvacuumspacetheCu(111)surface,bindingofthelonepairoftheNatomtobetweenneighboringslabsalongthe[111]direction.The45,463Cumeansthateachenantiomermaintainsitschirality.supercellsizesaredefinedtobe10.28×10.28×20.98ÅTofurthersupporttheseexperimentalfindings,DFTbasedonthePBE-optimizedCulatticeconstant(3.634Å).calculationsandSTMimagesimulationswereperformedtoThelowertwo-layerCuatomswerefixedatthebulkpositions,interrogatethebarriertorotationandtheappearanceoftheandtheuppertwo-layerCuatomswererelaxed.Thelong-moleculesintheSTMimages.DFT-derivedenergiesalongtherangeinteractionsamongneighboringslabsofCuwere43rotationalpathshowninFigure2Arevealthatthereisaverycorrectedusingdipolemomentsalongthe[111]direction.smallbarrier(14meV)fora60°rotationofthemoleculeAllcalculationswereperformedusinga2×2×1Monkhorst−44aroundtheN−CuaxeltothenextequivalentstableorientationPackk-pointmesh.TheinitialstructureofN-methylbutyl-ontheCu(111)surface.Thisexplainsthepseudo-hexagonalamineadsorbedontheCu(111)surfacewasoptimizeduntil−1shapeoftheindividualmoleculesintheSTMimagesthatforcesonatomswerelessthan0.02eVÅ.Rotationalbarriersoccurduetotimeaveragingofthesixequivalentstableandshapesofpotentialenergysurfacesfortherotationwereorientationsthatthemoleculerapidlyswitchesbetweenthederivedwithintherigid-rotorapproximationusingsingle-point29−31slowtimescaleofSTMimaging.Furthermore,theDFT-calculationsonimagesformedbyrotatinganoptimizedoptimizedstructuresenabledustomakeabsoluteassignmentsstructurefrom3to66°in3°intervals,withtheaxisofrotationofthechiralityofeachabsorbedmolecule.Specifically,FigureperpendiculartotheCu(111)surfaceandcenteredattheCu2BshowssimulatedSTMimagesoftheDFT-optimizedatomunderneaththeNatom.Therigid-rotorcalculationforstructuresinwhichthechiralityoftheadsorbedmoleculecantheintactrotoriscomparedtoanudgedelasticbandbedirectlyseenintheimage.TimeaveragesofthesecalculationintheSupportingInformation(FigureS4).projectionsoverthesixequivalentorientationsofthemoleculeonCu(111)yieldpinwheelshapesthatareinexcellent■RESULTSANDDISCUSSIONagreementwiththeSTMimagesoftherotatingmolecules.Figure1showsasummaryofSTMdataofN-methylbutyl-ThisallowsustousetheCahn−Ingold−PrelogrulesforaminedepositedonCu(111)at5Kandannealedto80KtoassigningchiralitytolabeleachisolatedmoleculeasRorS.equilibratethesystem.Figure1AshowsaschematicoftheTostudyelectricalexcitationofthesinglemolecules’molecularadsorptionsiteofN-methylbutylamineandillus-tunnelingcurrentversustime(Ivst),measurementswere3585https://dx.doi.org/10.1021/acs.jpcc.0c10767J.Phys.Chem.C2021,125,3584−3589
2TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleFigure2.(A)DFT-derivedenergiesasafunctionoftherotationanglefortheoptimizedN-methylbutylaminegeometrywiththeNatomatopaCuatom.Therotationofthismoleculeby60°wasenoughtocoverthewholerotationalpath.Thetop-viewschematicofN-methylbutylamineonCu(111)atdifferentanglesofrotationisshownbelowthegraph.(B)SimulatedSTMimageofanSenantiomerrotoroversixequivalentorientationsofthemoleculeonCu(111).ThebluespotindicatesthepositionoftheNatomcenter.AnSTMimageoftheSenantiomerisshownbelowforcomparison.SimulationSTMconditions:200mV,4.64Åtipposition.STMimagingconditions:20mV,200pA.Scalebar:0.5nm.Figure3.(A)Tunnelingcurrentasafunctionoftime(Ivst)tracesforN-methylbutylamineonCu(111)revealssixdiscretetunnelingcurrentvaluesthatcorrespondtothesixinequivalentorientationsofthemolecule(red,blue,green,purple,orange,andyellow)withrespecttothepositionoftheSTMtippositionasmarkedbytheblackcrosssymbol.Thelargerlobesintheschematicindicatethebutylgroupposition,whilethesmallerlobesindicatethemethylgrouppositionoftherotor.Excitationconditions:400mV,100pA.(B)ActionspectraforN-methylbutylamineonCu(111)atasettunnelingcurrentof10pAshowingasharpincreaseintherotationrateabovethe360mVthresholdvoltage,regardlessofthepositive/negativebias.(C)Plotofrotationratevstunnelingcurrentforvariousappliedvoltages.Thelinesarepowerlawfitstothedata;ngivestheelectronorder,i.e.,onevsmultipleelectron-inducedrotation.takeninwhichtheSTMtipispositionedofftothesideofoneequivalentorientationsofthealkyltail(asshownintheofthelobesofthepinwheelshapeoftherotatingmoleculeschematicinFigure3AwheretheSTMtippositionismarkedwiththefeedbackloopoffandthetunnelingcurrent(I)withan“X”).Thesesixtunnelingcurrentlevelsarisefromtherecordedovertime(t).AscanbeseeninFigure3A,thesepositionofthemolecularlobeswithrespecttotheSTMtip;tracesshow“long”periodswherethemoleculeisinonetheshorterthedistancebetweenthetipandrotor,thehigherorientation(i.e.,onetunnelingcurrentvalue)separatedbythetunnelingcurrent.Thesesingle-pointmeasurementsallow“fast”switchingbetweenthesixdifferentrotationalorienta-ustoquantifyrotationratesofsinglemolecules.Furthermore,tions.ThesesixtunnelingcurrentscorrespondtothesixbyrecordingtheseIversusttracesasafunctionofapplied3586https://dx.doi.org/10.1021/acs.jpcc.0c10767J.Phys.Chem.C2021,125,3584−3589
3TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticlevoltage,itenablesustoplotactionspectrathatrelatetherateenantiomer,asseeninFigure4A.Tofurtherdemonstrateofanaction(inthiscase,arotationratethatreferstoanythiseffect,westudiedsixenantiomersofthemoleculesisolatedmolecularrotationbetweenthesixequivalentorientations)totheenergyofthetunnelingelectrons(asdefinedbythevoltageacrossthetunneljunction).TheactionspectruminFigure3Bshowsasharpincreaseoftherotationratearound360mV,regardlessofthedirectionofelectronflow.Thisisacharacteristicofinelasticelectrontunnelingbywhichanelectronwithanenergyatorgreaterthanthemolecularvibrationmodequantaitcouplestocanleadtothemotionof47−49themoleculeasawhole.Todeterminewhethertheelectricalexcitationoftherotationalmotionisaone-ormulti-electronprocess,thetunnelingcurrent(I)dependenceoftherotationrate(k)was47studied,andtherotationrateisplottedasafunctionofthetunnelingcurrentnkI=inwhichnreferstothenumberofelectronsagivenprocess47involves.TheresultsinFigure3Cshowthat,atorbelow350mV,rotationalexcitationisamulti-electronprocessversusaone-electronprocessat400mV.This,inconjunctionwiththeactionspectroscopyresultsthatshowasharpincreaseinFigure4.Plotsofthe(A)tunnelingelectron-inducedrotationrateofrotationrateat∼360mV,indicatesthattheprimarypathwayRandSenantiomersofN-methylbutylaminewithdifferentSTMtips;forelectricalexcitationoftherotoroccursviaexcitationofC−theRrotorisrepresentedinred,andtheSrotorisrepresentedinHstretchmodesthatoccuratthisenergy.47,48Excitationoftheblue.(B)Rotationrateratios(RateR/RateS).Excitationconditions:400mV,100pA.Errorbarsreflectonestandarddeviation.N−HmodeofthemoleculecanberuledoutasN−Hstretchesinaminesthatoccurintherangeof3300−3500cm−1,whichwouldleadtoanonsetvoltageof410−430fromeachotherinthesameareaofthesurfacewiththesamemeV.50STMtipstate.Specifically,FigureS3demonstratesthattheWhencomparingtheenergyinput(360meVelectron)tointeractionoftheSTMtipwiththethreeSenantiomersleadsthebarriertorotationinwhichDFTputsat∼14meV,onecantoaslow(∼2Hz)rotationrateversusthesameSTMtipintheseethatthereisasignificantdifferenceinenergybetweenthesametipstateinteractingwiththeRenantiomers,whichleadsinputandoutputchannels.Thesebarrierestimatesandtoafaster(∼8Hz)rate.ThisdatadefinitivelydemonstratesrotationratesareinfluencedbyentropyeffectsandfinitethattheinteractionbetweentheSTMtipandthechiraltemperaturecorrections,20butsucheffectsarelesssignificantmoleculesisdifferentdependingiftheRorSenantiomerisatlowtemperatureandcannotaccountforamismatchofoverprobedandaclassicdiastereomericrelationshipisobserved.oneorderofmagnitude.Thismismatchbetweenhigh-energyGiventhattherotationalratedifferencesarephysicalvibrationalmodesthatdrivethelowenergyrotationalmotionpropertiesofthesystem,theSTMtipitselfmustbechiralto27,62hasbeenobservedinmolecularsystemsbeforeandarisesfrominducethisdiastereomerism.Toaidinthiscomparison,theC−Hvibrationalmodeshavingahighinelasticexcitationtheratiooftherotationalrates(RateR/RateS)fordifferentcrosssectionforexcitationfollowedbyenergytransferviaSTMtipsisshowninFigure4B.Statisticallysignificantratiosanharmoniccouplingofthesehigh-energyvibrationalmodestoabove1.0representSTMtipsthatarechiralandfavorlowerenergyrotationalandfrustratedtranslationalexcitationoftheRenantiomer,whileratiosbelow1.0representmodes.51−54ThisalsoindicatesthattherateofvibrationalSTMtipsthatfavorexcitationoftheSenantiomer.RatiosrelaxationviaenergytransfertotheCu(111)surfaceoccurscloserto1.00comefromSTMtipswithnomeasurableslowlyenoughtoallowtheIVRcouplingthatleadsthechiralityastherotationrateofbothenantiomersisequalrotationtooccur.54−59withinerror.Noevidenceforpreferentialrotationinonedirectionwasobserved,whichisconsistentwithsymmetricrotationbarriers■CONCLUSIONSintheDFTderivedenergiesinFigure2,andisincontrastwithAcombinedSTMandDFTstudyofanewmolecularrotorothersurface-adsorbedmoleculeswithasymmetrictorsionalsystemconsistingofindividualN-methylbutylaminemoleculesbarriersthatproducenetdirectionalityintheirrotationwhenboundtoaCu(111)surfaceisreported.Rotationaroundthe27,60,61electricallyexcitedbySTMtips.However,whenN−Cubondgivesincreasetothechiralpinwheelappearancemeasuringtheelectricallyinducedrotationratesofthetwoofindividualrotatingmolecules,andourcomplementaryDFTenantiomersofthemoleculeunderidenticalexcitationcalculationsenablethechiralityofeachindividualmolecularconditions(i.e.,sametunnelingvoltage,tunnelingcurrent,rotortobeassigned.Theresultspresentedindicatethattheandsampletemperature),statisticallysignificantdifferencesinrotationofthemoleculescanbedrivenbytunnelingelectronstherotationrateofthetwoenantiomersofthemoleculewerewithanenergyof360meVorgreaterinaone-electronobserved.BychangingtheSTMtipbetweenmeasurementsviaprocess.Importantly,significantdifferencesintherotationhighvoltagepulsesorsurfaceindentation,someSTMtipswereratesofRandSenantiomersofthemoleculewereobserved,observedtoinducefasterrotationoftheRenantiomeroftheanditwasfoundthatthesedifferenceschangeastheSTMtiprotor,whileothertipsinducefasterrotationoftheShaschanged.Theseresultshighlightthediastereomerism3587https://dx.doi.org/10.1021/acs.jpcc.0c10767J.Phys.Chem.C2021,125,3584−3589
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