Enhanced Gating Performance of Single-Molecule Conductance by Heterocyclic Molecules - Wang et al. - 2021 - Unknown

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pubs.acs.org/JPCLLetterEnhancedGatingPerformanceofSingle-MoleculeConductancebyHeterocyclicMolecules##Ya-HaoWang,FengYan,Dong-FangLi,Yan-FengXi,RuiCao,Ju-FangZheng,YongShao,ShanJin,*Jing-ZheChen,*andXiao-ShunZhou*CiteThis:J.Phys.Chem.Lett.2021,12,758−763ReadOnlineACCESSMetrics&MoreArticleRecommendations*sıSupportingInformationABSTRACT:Enhancingthegatingperformanceofsingle-moleculeconductanceissignificantforrealizingmoleculartransistors.Herein,wereportanewstrategytoimprovetheelectrochemicalgatingefficiencyofsingle-moleculeconductancewithfusedmolecularstructuresconsistingofheterocyclicringsoffuran,thiophene,orselenophene.Oneordermagnitudeofgatingratioisachievedwithinapotentialwindowof1.2Vfortheselenophene-basedmolecule,whichissignificantlygreaterthanthatofotherheterocyclicandbenzeneringmolecules.ThisiscausedbythedifferentelectronicstructuresofheterocyclicmoleculesandtransmissioncoefficientsT(E),andpreliminaryresonancetunnelingisachievedthroughthehighestoccupiedmolecularorbitalathighpotential.ThecurrentworkexperimentallyshowsthatelectrochemicalgatingperformancecanbesignificantlymodulatedbythealignmentoftheconductingorbitaloftheheterocyclicmoleculerelativetothemetalFermienergy.abricatingsingle-moleculedeviceshasbeentheultimateTherefore,thesefusedstructureswithdifferentheterocyclicFgoalofelectronicdeviceminimizationsinceAviramandringsmaybealsoappliedtooptimizethegatingefficiencyof1−4electrontransportatthesingle-moleculelevel,butnocasehasRatnerproposedaprototypemolecularrectifierin1974.Benefitingfromthedevelopmentofthesingle-moleculebreakbeenreportedtodate,andaclearcorrelationbetweenthejunctiontechnique,numerousinvestigationshavesuccessfullystructuresofheterocyclicmoleculesandelectrochemicalgatingconstructedandexploredmetal−molecule−metaljunctionsremainsambiguous.overthepasttwodecades.5−9Todate,electrontransportInthiswork,wedesignedandsynthesizedaseriesofthroughsinglemoleculescouldbetunedunderexternalheterocyclicmoleculesoffuran(BT-O),thiophene(BT-S),stimulus,suchaselectricity,10,11light,12−14andpH.15−17andselenophene(BT-Se)connectingdihydrobenzo[b]-DownloadedviaBUTLERUNIVonMay16,2021at06:42:59(UTC).thiophene(BT)throughanethynylspacer.Single-moleculeAmongthem,electrochemicalmodulationprovidesapromis-ingmethodformanipulatingtheenergyalignmentbetweenconductancedependingonappliedgatepotentialsissystem-molecularfrontierorbitalsandFermilevelofmetalelectro-aticallyinvestigatedbyelectrochemicalscanningtunnelingdes.10,18−20Significantresults,suchasredox-enhancedmicroscopybreakjunctions(ECSTM-BJ)in1-butyl-3-Seehttps://pubs.acs.org/sharingguidelinesforoptionsonhowtolegitimatelysharepublishedarticles.tunneling,10,21−24moleculestructuretransforms,25andquan-methylimidazoliumhexafluorophosphate(BMIPF6).Com-tuminterference26,27viaelectrochemicalgating,havebeenbinedwithDFTcalculation,theenhancedgatingratioofconductanceisanalyzedanddiscussedwiththeenergyreported.Inordertorealizefunctionallyelectroniccompo-alignmentbetweenmoleculesandelectrodesandtransmissionnentslikeasingle-moleculeswitchortransistor,mucheffortspectra.Thesingle-moleculeconfigurationfortheroom-hasbeendevotedtoimprovinggatingefficiencyoftemperatureelectrochemicalgatingisconstructedbyECSTM-conductancewithinthelimitedgatepotentialrange,butit21,27BJandschematicallyillustratedinFigure1a.Briefly,theremainsanoutstandingchallenge.encapsulatedAutipandAu(111)substrateactassourceandTypically,theintrinsicpropertyofmolecularstructuredrainelectrodes,whilethePtcounterandreferenceelectrodesgreatlydeterminestheelectrontransportthroughthemetal−28−30serveasgateelectrodes.Withabipotentiostatsetup,themolecule−metaljunction.Recently,moleculeswithfusedstructuresconsistingoforganicbackbonesandheteroa-toms31−35havereceivedwideattention,becausethedoping-Received:November17,2020likeheteroatomsofferauniqueopportunitytomodifyorganicAccepted:December30,2020moleculematerialsandelectrontransportpathways.36ForPublished:January6,2021example,insertingfive-memberedheterocyclicringsinthemolecularbackbonecouldchangethemoleculararomaticity37−39andmodulatethequantumeffectofelectrontransport.©2021AmericanChemicalSocietyhttps://dx.doi.org/10.1021/acs.jpclett.0c03430758J.Phys.Chem.Lett.2021,12,758−763

1TheJournalofPhysicalChemistryLetterspubs.acs.org/JPCLLetterFigure1.(a)Schematicdiagramofelectrochemicalgatingsingle-moleculeconductanceofheterocyclicmoleculesbySTM-BJ.(b)InvestigatedmolecularstructureofBT-O,BT-S,andBT-Se.Figure2.(a)Representativeconductance−distancetraces(b)andone-dimensionalconductancehistogramofBT-Omeasuredatdifferentgatepotentialswithabiasvoltageof50mV(Esubstrate−Etip).Theconductancepeakcountsarenormalizedbythenumbersofconductancecurvesused.electrochemicalpotentialoftheSTMtipandsubstratecouldsimultaneouslychangedwithafixedbiasof50mV.Accordingbeindependentlycontrolled,andthepotentialdifferencetothecyclicvoltammetryofBT-OonAu(111)inBMIPF6betweenthesetwoelectrodesisthebiasvoltageappliedtothe(FigureS1),thegatepotentialisshiftedfrom−0.9to0.3Vvsmolecularjunction.Theionicliquid(IL)ischosenasPt,whichislimitedbythemoleculardesorptionatnegativeelectrolyteforgatingsingle-moleculeconductance,becauseitvoltageortheoxidationofAuatpositivevoltage.Figure2a18hashighcouplingefficiencywithappliedelectricfield.showstherepresentativeconductance−distancetracesofBT-Figure1bshowsthestructureofinvestigatedmolecules,Oobtainedatdifferentpotentialsofsubstrate,andthesewhicharesynthesizedaccordingtoproceduresdetailedintheplateaufeaturescorrespondtotheformationofmolecular18SupportingInformation.Allmoleculesarepurifiedbyusingjunctions.Clearly,theconductancevaluesincreasefromcolumnchromatographyandcharacterizedbyhigh-resolution10−4.2(6.3×10−5)to10−3.4(4.0×10−4)G(G=2e2/h)as00massspectrometryandNMR.Thetriplebondsmaketheseelectrochemicalpotentialspositivelyscan.Thisindicatesthatmoleculeshavesimilarinternaltorsionangle,whilethetheelectrontunnelingispredominantlythroughthehighestanchoringgroupofBTprovidesauniformbindinggeometryoccupiedmolecularorbitals(HOMOs)ofBT-O,similarto40,4140betweenmoleculeandelectrode,whichresultsinauniquereportedmoleculeswiththesameanchoringgroups.distributionofconductancevalueduringthebreakjunctionTodeterminetheconductancevaluedependingongatemeasurement.Thecyclicunitistheonlydifferenceamongpotential,wealsoconstructone-dimensionalhistogramsinathesemoleculesandallowsustoinvestigatetheimpactofthestatisticalmannerfromthousandsoftraceswithoutanyfive-memberedringonthemodulationofelectrontransportselection.AsshowninFigure2b,thewell-definedpeaksagainstelectrochemicalgatepotentials.coincidewiththestepvaluesinFigure2a.Fromtheplots,itisInordertostudytheconductancegatingbehaviorofobviousthattheconductanceofBT-Ochangesfrom6.3×molecularjunctions,weperformtheconductancemeasure-10−5to4.0×10−4Gwithanincreaseofthegatepotentialby0mentinahigh-purityN2atmosphereatroomtemperature.1.2V,givingoutarelativeconductancevariationof635%.ItisThepotentialsoftarget-moleculecoveredAu(111)andtipareabout6timesgreaterthanthatof1,2-bis(4,4-dimethylth-759https://dx.doi.org/10.1021/acs.jpclett.0c03430J.Phys.Chem.Lett.2021,12,758−763

2TheJournalofPhysicalChemistryLetterspubs.acs.org/JPCLLetterFigure3.One-dimensionalconductancehistogramof(a)BT-Sand(b)BT-Semeasuredatdifferentgatepotentials.Theconductancepeakcountsarenormalizedbythenumbersofconductancecurvesused.(c)Single-moleculeconductanceofmoleculesdependsonthegatepotential.(d)Summaryhistogramsofgateratioofconductance.iochroman-6-yl)ethylenehavingabenzeneringinsteadof−0.9to0.3V;theconductancevaluesincreasefrom8.9×10−5furan.42Forcomparison,wealsoperformconductanceGto6.3×10−4Gwithagatingratioof708%forBT-Sand00measurementofBT-C(benzeneringinsteadoffuran)at1.2×10−4Gto1.2×10−3Gwithagatingratioof1000%for00differentpotentials(FigureS2),andtheconductancegatingBT-Se.Thisindicatesthatthetypeofheterocyclicringhasaratiois282%,whichis2.3timeslessthanthatofBT-O.greatimpactontheelectrochemicalmodulationofcon-Torevealpossiblereasonsfortheoptimizedgatingratio,theductance.Particularly,theoneorderofmagnitudecontinuouselectronicstructuresofthesefreeBT-CandBT-OaremodulationoftheconductancevalueobservedatBT-SeisanalyzedbyDFTcalculationontheGaussian09softwarecomparabletothegatingratioofelectrochemicalcontrolled4331package(Figure3).Accordingtopreviousreports,thequantuminterferenceatanthraquinone-basedmolecules.intrinsicfrontiermolecularorbitalssignificantlyaffectenergyThus,theseπ-conjugatedmoleculesimplantingwithdifferentalignmentwithmetalelectrodesanddeterminateconductancefive-memberedheterocyclicringsprovidesapromising44,45ofmolecularjunctions.Theoptimizedmolecularstruc-molecularmaterialtoenhancethegatingperformanceofturesaredisplayedinFigureS3.WefindthattheHOMOsandsingle-moleculeconductance.lowestunoccupiedmolecularorbitals(LUMOs)are−5.72andWealsoquantitativelystudytheelectronicstructuresof−1.71eVforBT-Cand−5.20eVand−1.89eVforBT-O.theseisolatedheterocyclicmolecules.SimilartoBT-O,theObviously,replacingthephenylringwithfuranintheenergydiagramsinFigureS3providetheLUMOat−2.07andmolecularbackbonecouldlargelyincreasetheHOMOby−2.16eVandHOMOat−5.24and−5.23eVforBT-Sand0.52eVandgreatlydiminishtheenergybarrierofEF−EHOMOBT-Se,respectively.TheHOMO−LUMOgapdecreasesinaswellastheenergygapofELUMO−EHOMO.AstheHOMOstheorderBT-Se(3.07eV)

3TheJournalofPhysicalChemistryLetterspubs.acs.org/JPCLLetterFigure4.(a)ExperimentalconductanceandcalculatedT(E)forBT-O,BT-S,andBT-SeasafunctionoftheappliedgatingpotentialvsPt.(b)TheschematicdiagramofelectrochemicalgatingmechanismfornonredoxactivemolecularjunctionsinILs.T(E)dependontheenergylevelofmolecularorbitalsrelativetypecontinuousmodulationbehaviorofelectrontransporttotheFermileveloftheelectrode(E−EF).Obviously,thethroughBT-O,BT-S,andBT-SeisobservedfortheseorderofT(E)aroundE=EFfollowsBT-Se>BT-S>BT-O,nonredoxactiveheterocyclicmoleculesupontheincreasingwhichiswellconsistentwithexperimentalobservationofthegatepotential.Quantitatively,theorderoftheconductancelargestconductancevalueatBT-Se.gateratiofollowsBT-Se(1000%)>BT-S(708%)>BT-OTypically,electrochemicalgatingofsingle-moleculejunc-(635%)>BT-C(282%)inthegatingpotentialrangeof1.2V.tionsisrealizedbyapplyingpotentialonelectrode,whichcanWiththehelpofDFTcalculations,thesignificantimprove-shifttheFermileveloftheelectroderelativetothefrontiermentofconductancegatingratioisattributedtothedifferentorbitalsofmoleculesatthesolid−liquidinterface(Figureelectronicstructuresofheterocyclicmoleculesandtrans-4b).18,21,46,47Qualitatively,theEofelectrodesmovesclosertomissioncoefficientsT(E).ThecurrentworkprovesthattheFEHOMOofmoleculesasthepotentialincreases,leadingtolowerheterocyclicbackbonescanenhancethegatingperformanceenergybarrierheightforelectrontunnelingthroughtheandcanbeusedtodesignahigh-performancemolecularHOMO.Quantitatively,theEFofAusubstratecouldbedevice.calculatedaccordingtotheformulaEF=−4.66−Epotential,whereEpotentialistheappliedpotentialand−4.66eVisthe■ASSOCIATEDCONTENTenergylevelofPtreferenceelectrodedeterminedbyusingthe*sıSupportingInformationredoxpotentialofferrocene(F+/F)asthestandardinTheSupportingInformationisavailablefreeofchargeatccBMIPF(detailsinFigureS5).27Itisreportedthattheworkhttps://pubs.acs.org/doi/10.1021/acs.jpclett.0c03430.6functionis4.3eVforAucoveredwithself-assembledExperimentaldetailsandmoreexperimentaldataof27monolayers.Thus,theelectrodepotentialisestimatedtoconductancehistograms,molecularstructure(PDF)be−0.36VvsPtatE=EF,andthevariationoftheoreticalT(E)inFigure4aiscomparabletotheexperimental■conductanceatdifferentgatepotentials.TheexperimentalAUTHORINFORMATIONCorrespondingAuthorsconductanceminimumisnotobserved,whilethereisaXiao-ShunZhou−KeyLaboratoryoftheMinistryofconductanceminimumintheoreticalresults.ThisdiscrepancyEducationforAdvancedCatalysisMaterials,InstituteofbetweenexperimentalandtheoreticalresultsmightarisefromPhysicalChemistry,ZhejiangNormalUniversity,Jinhuathesimulatedmodelsignoringtheelectrochemicalionsand321004,China;orcid.org/0000-0003-1673-8125;solvents,andtheexperimentalminimummaybefoundinEmail:xszhou@zjnu.edu.cnmorenegativepotentials.However,thedesorptionofthoseShanJin−KeyLaboratoryofPesticideandChemicalBiology,moleculeshappensinthissituation,andthesingle-moleculeMinistryofEducation,CollegeofChemistry,CentralChinaconductancemeasurementcannotbecarriedout.Interestingly,NormalUniversity,Wuhan430079,China;orcid.org/theconductancevalueofthesethreeheterocyclicmolecules0000-0002-1070-5456;Email:jinshan@mail.ccnu.edu.cnexponentiallyincreasesabove0V,whichmightarisefromJing-ZheChen−DepartmentofPhysics,ShanghaiUniversity,preliminaryresonancetunnelingastheEF−EHOMOshrinkstoShanghai200444,China;orcid.org/0000-0002-0003-reachstrongalignmentbetweenelectrodeandadsorbed3457;Email:jingzhe@shu.edu.cnmolecules.Thus,theheterocyclicmoleculeswiththeuniqueintrinsicpropertiesofferagoodmaterialforenhancinggatingAuthorsefficiencyofsingle-moleculeconductance.Ya-HaoWang−KeyLaboratoryoftheMinistryofEducationInconclusion,thenewstrategyofusingfive-memberedforAdvancedCatalysisMaterials,InstituteofPhysicalheterocycliccompoundsissuccessfullyappliedtoimprovetheChemistry,ZhejiangNormalUniversity,Jinhua321004,electrochemicalgatingofsingle-moleculeconductance.Ap-China;orcid.org/0000-0001-5943-8646761https://dx.doi.org/10.1021/acs.jpclett.0c03430J.Phys.Chem.Lett.2021,12,758−763

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