Table Of Content

Advances in Atom and Single Molecule Machines Series Editor: Christian Joachim Francesca Moresco Christian Joachim Editors Single Molecule Mechanics on a Surface Gears, Motors and Nanocars Advances in Atom and Single Molecule Machines SeriesEditor ChristianJoachim,GNS,CNRS,ToulouseCedex,France EditorialBoard LeonhardGrill,InstitutfürChemie,Karl-Franzens-UniversitätGraz,Graz, Steiermark,Austria FedorJelezko,InstituteofQuantumOptics,UlmUniversity,Ulm, Baden-Württemberg,Germany MasanoriKoshino,ChemistryandMaterials,NationalInstituteofAdvanced IndustrialScienceandTechnology,Tsukuba,Ibaraki,Japan DavidMartrou,NanosciencesGroup,Centred’ÉlaborationdeMatériauxet d’EtudesStructurales,Toulouse,France TomonobuNakayama,NationalInstituteforMaterialsScience,Tsukuba,Ibaraki, Japan GwénaëlRapenne,Centred’ÉlaborationdeMatériauxetd’EtudesStructurales, Toulouse,France FrançoiseRemacle,Chemistry,UniversityofLiege,Liège,Belgium AdvancesinAtomandSingleMoleculeMachinesisthefirstcomprehensiveseries ofbooksdealingspecificallywithsingleatomandmoleculemachines.Derivedfrom a number of long-term European Commission Future and Emerging Technologies (FET)projectsincludingAtMol,Elfos,Focus,Diamant,Artist,PAMSandMEMO, volumesinthisseriescomprisetopicalreviews,lecture-coursederivedtextbooksand re-workedproceedingsofworkshops. · Francesca Moresco Christian Joachim Editors Single Molecule Mechanics on a Surface Gears, Motors and Nanocars Editors FrancescaMoresco ChristianJoachim CentreforAdvancingElectronicsDresden Pico-LabCEMES-CNRS TechnischeUniversitätDresden Centred’ÉlaborationdeMatériauxet Dresden,Sachsen,Germany d’EtudesStructurales Toulouse,France ISSN 2193-9691 ISSN 2193-9705 (electronic) AdvancesinAtomandSingleMoleculeMachines ISBN 978-3-031-16929-8 ISBN 978-3-031-16930-4 (eBook) https://doi.org/10.1007/978-3-031-16930-4 ©TheEditor(s)(ifapplicable)andTheAuthor(s),underexclusivelicensetoSpringerNature SwitzerlandAG2023 Thisworkissubjecttocopyright.AllrightsaresolelyandexclusivelylicensedbythePublisher,whether thewholeorpartofthematerialisconcerned,specificallytherightsoftranslation,reprinting,reuse ofillustrations,recitation,broadcasting,reproductiononmicrofilmsorinanyotherphysicalway,and transmissionorinformationstorageandretrieval,electronicadaptation,computersoftware,orbysimilar ordissimilarmethodologynowknownorhereafterdeveloped. Theuseofgeneraldescriptivenames,registerednames,trademarks,servicemarks,etc.inthispublication doesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexemptfromtherelevant protectivelawsandregulationsandthereforefreeforgeneraluse. Thepublisher,theauthors,andtheeditorsaresafetoassumethattheadviceandinformationinthisbook arebelievedtobetrueandaccurateatthedateofpublication.Neitherthepublishernortheauthorsor theeditorsgiveawarranty,expressedorimplied,withrespecttothematerialcontainedhereinorforany errorsoromissionsthatmayhavebeenmade.Thepublisherremainsneutralwithregardtojurisdictional claimsinpublishedmapsandinstitutionalaffiliations. ThisSpringerimprintispublishedbytheregisteredcompanySpringerNatureSwitzerlandAG Theregisteredcompanyaddressis:Gewerbestrasse11,6330Cham,Switzerland Preface Mechanics with a single molecule starts with a dimer: vibrating, rotating, flying randomlyandpossiblydissociatinginthegasphase.Adsorbedonasurface,sucha dimercanalsovibrate,rotate,desorbordissociate.Preservingthedimerintegrityon thesurfacerequiresthatitselectronicwavefunctionisintrinsicallycoherentwhile itsmechanicaldi-nuclearwavefunctioncanbepreservedornot.Onasurface,this mechanicalwavefunctionbecomessemi-classicalbydecoherence.Here,vibration androtationarethereforebecomingclassical. Thisbookisaboutthemechanicsoflargermulti-atomicmolecules,largeenough that their collective mechanical motions become almost classical by themselves. Goingfromadimertosuchlargemoleculeopensthepathtodesignsinglemolecule mechanical machinery. When adsorbed on a proper metallic surface, it is known that already a single PF3 molecule can alone works like a single molecule-gear (See Volume 13 of this series). While remaining well below the number of atoms entering in the chemical composition of a protein but increasing this number in a covalent manner from the PF3 molecule to, for example, 50 to 100 atoms, then a singlemoleculecanbecomealoneonasurfaceamolecule-wheel,amolecule-gear, a molecular train of gears, a molecule-motor, a molecule-car or even a molecular mechanicalcalculator. Thisbookpresentsdifferentexamplesofsinglemoleculemechanicalmachinery, eachmoleculefunctioningoneatatimewhileadsorbedonasurface.Thisfunctioning (randomornot?)canbemadepossiblebytheenergyextractedfromthesurfaceby the molecule alone or using part of the energy provided using the atomic apex of the tip of a scanning tunneling microscope. This book results from the MEMO workshop“SingleMoleculeMachinesonaSurfaceGears,TrainofGears,Motors, andCars”heldinToulouse(France)duringNovember24–25,2021.Italsoresults from the second International Nanocar Race II organized in Toulouse by MEMO duringtheMarch24–25,2022.Mechanicswithmolecules(MEMO)wasanH2020 FETEuropeanprojectfrom2017to2022. We have regrouped in this volume general considerations concerning single molecule mechanics on a surface like unidirectional motion, the corresponding molecular synthesis and the required surface adsorption calculations. Four teams v vi Preface having participated to Nanocar Race II are presenting their molecule-vehicles and thestoryrelatedtotheirdesign.Wearehonoredtohavereceivedthecontributionof thetwowinnersoftheracedescribingtheirdesignandtheirdrivingontheAu(111) surface.Finally,wehavechosenthreepossibletopicalapplicationsofsinglemolecule mechanics on a surface: the functioning of a molecular mechanical calculator, the simulationofwhatwillbethetransmissionofrotationbetweenasolid-statenanogear andamolecule-gearandfinallyonepossible2Dself-assemblyarchitectureforsingle molecule machinery, each molecule being well isolated in the surface nanoporous molecularnetwork. We expect that this new volume of the series concerning single molecule mechanicsanditsrelatedfunctioningmachinerywillencouragethereaderstoenter inthedesignofnewmoleculesormolecularmachinery.Thiswillbeagoodopportu- nitytoexplorethemixingbetweenquantumandsemi-classicaldesignofmechanical nanomachinesandmaybetoproposenewmolecularstructuresofmolecule-vehicles forNanocarRaceIII. We thank the European Commission H2020 FET program for the MEMO and Nanocar Race II financial supports, the C’Nano for the co-organization of the November2021ToulouseworkshopatTheP.Baudiscongresscenter.Averyspecial thanks to the CEMES-CNRS and TU-Dresden personnel for their contribution to the organization of Nanocar Race II in March 2022 and certainly to the Webcast IN2P3-CNRS teams (and their affiliates) for their fantastic job before (November 2021),duringandafterNanocarRaceIIinhandlingtheliveHDtransmissionofthe competition. Dresden,Germany FrancescaMoresco Toulouse,France ChristianJoachim Contents UnidirectionalMotionofSingleMoleculesatSurfaces ................ 1 GrantJ.SimpsonandLeonhardGrill DMBI—fromn-TypeDopanttoMolecularMachines ................. 29 OumaimaAiboudiandFranziskaLissel Assembly,DiffusionandRotationofOrganicMoleculesonaGold Surface ........................................................... 41 RobertoRobles,VladimírZobacˇ,andNicolásLorente FromEarlyPrototypestoOn-SurfaceDrivableSingleMolecule Nano-vehicles ..................................................... 59 Henri-PierreJacquotdeRouville,SoniaAdrouche,XavierBouju, Jean-PierreLaunay,GwénaëlRapenne,andChristianJoachim On-SurfaceTranslationalActivityofPorphyrinChromophore Molecules ......................................................... 83 JonathanP.Hill,DanielT.Payne,KeweiSun,YoshitakaMatsushita, AyakoNakata,PuneetMishra,TakashiUchihashi,WakaNakanishi, KatsuhikoAriga,TomonobuNakayama,andShigekiKawai Controlled Driving of a Single-Molecule Anthracene-Based NanocaronaMetalSurface ........................................ 105 AnaBarragán, KoenLauwaet, TomásNicolás-García, AnaSánchez-Grande, JoséIgnacioUrgel, JonasBjörk, EmilioM.Pérez,andDavidÉcija AzuleneBasedNanocars ........................................... 121 TimKühne, KwanHoAu-Yeung, SuchetanaSarkar, andFrancescaMoresco TowardsaMolecularMechanicalCalculator ......................... 141 We-HyoSoeandChristianJoachim vii viii Contents AtomisticModellingofEnergyDissipationinNanoscaleGears ........ 157 Huang-HsiangLin, AlexanderCroy, RafaelGutierrez, andGianaurelioCuniberti MolecularNetworksandSurfaceEngineeringforSingleMolecule Studies:FromSpatialSeparationtoEmergentProperties ............. 177 R.S.KoenHoutsmaandMeikeStöhr Unidirectional Motion of Single Molecules at Surfaces Grant J. Simpson and Leonhard Grill Abstract It is a basic concept of physical chemistry that in thermal equilibrium every individual process is compensated by its reverse process, which is called microscopic reversibility. It is therefore a challenge to realize unidirectional motion of atoms and molecules. Here, various examples of unidirectional motion at surfaces are presented, which cover both rotation and translation of single molecules. Two ways to achieve unidirectionality are discussed. First, the presence of a local gradient that deforms the potential energy surface and leads to unidirectionality. This can be caused by the tip of a scanning tunneling microscope, which is also a very suitable instrument to follow the motion of individual molecules. Second, intrinsic unidirectionality of a molecule-surface system, which is of particular interest to be employed in molecular machines for useful work at the atomic scale. · · · Keywords Unidirectionality Microscopic reversibility Surfaces Molecular · · · · motors Rotation Translation Scanning tunneling microscopy (STM) · · · Single-molecule manipulation Adsorption Single-crystals · · · Surface-molecular-beam Potential energy surface Molecular machines Mechanics with molecules 1 Unidirectionality Caused by Local Gradients The motion of molecules at solid surfaces is dictated by the potential energy surface (PES) that is determined by the interaction between adsorbate and substrate. In the case of the commonly used single-crystal surfaces, which are well-defined and thus facilitate molecular dynamics studies of model systems, the PES shape reflects their periodic lattice. Scanning tunneling microscopy (STM) is a very suitable method to study such systems. One the one hand, this is because it can image single molecules with high spatial resolution to reveal intramolecular details. On the other hand, it can be used to controllably deform the potential energy surface via the forces that are B G. J. Simpson · L. Grill ( ) Department of Physical Chemistry, University of Graz, Heinrichstrasse 28, Graz, Austria e-mail: [email protected] © The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 1 F. Moresco and C. Joachim (eds.), Single Molecule Mechanics on a Surface, Advances in Atom and Single Molecule Machines, https://doi.org/10.1007/978-3-031-16930-4_1