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A此icle

EetofoecuapackgonFedE什ecperfomaceOsngrysasofThenysubsuedpyenes

MinoruAshizawa,KoichiYamada,AtsukoFukaya,ReizoKato,KoujiHara,andJunTakeya

Chem.A,1ater.,2008,20(15),48834890・D01:10.102νCm703499q・publicationDate(vveb):28June2008

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ノ《、Acspublications'^'Hi帥quali可Hi8himpad. ChemistryofMヨterialsispublishedbytheAm引icanchemlcalsociety.1'155

SixteenthstreetN.VV..VV日Shington,DC20036

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EffectofMolecularpacMngonField・EffectperformanceofsingleCrystalsofThienyl.subst並Utedpyrenes

ReizoKato,*'1KoujiHara,andYamada,ゞAtsukoFukaya,ナ入lh)ONAshizawa*,1,キKoicN

JunTakeya*'

C011denseduoleCιι1α1'uatιrialSιαhoratorv,RlkΞN,2-1,Hhosawa,wako・shi,saitamα351-019&ノαPι1π,

USRι,CR1ΞPI,2・/1-1,κ0"1αι,70b,0201-85ノノ,j4Pα11,απdDepaπ1陀eπtqi'che挽istly,Graduatescho01Ojscie11Ce,osak4Uπiuersily,Toyohakα560-0043,ノαPαπ

ReceiuedDιCι1πber8,2007.ReuisedUα111ιSCI'il)1Receiueduay20,2008

10.102νCm703499qccc$40.75@2008AmedC即Che血CalsociewhbⅡShedonweb06/28/2008

Che"1.ualer.2008,20,48834890

AsedesofpyrenedehvalivescontainingthienylgTOUPS,1-3,hasbeenpreparedusing小esuzuMCouplingreaclion.RecryS稔IHzationfl'omsoluljonandphysicalvaporlra11Sporl(PVT)melhodafl"ordeddifferenttypesofcrystalsofl.Fromthe111ixtureofisomersof2,thel,8・isomerpreferablycryst址lizedfromsolution,whereasthel,6・isomercrystalwasobtainedbythepvTmethod.Fabricatingsingle・CTysta】-based介eld-e仟ecttransistorsoftheabovecompouT】dswedirectlycomparedthe6eld-e仟ectPerformancebetweenthedevicesofthetwoisoformsof1帥d血Oseofthetwoisomersof2.Though伽eOverlapintegralswerecalculatedtobeonly~10ーキ,血ebestholemobilityreachedo.02Cm2V-1S-1forOneofthesin31ecrystalsofl.1n住i塵Uingly,fotb0血la11d20nlyonetypeof血ecrystalshowS山e6eld・e丘ectcharacteristics,indicating杜lesi容ni員Ca11CeofmolecularpacMngeven血theabsenceofb鬮d柱如Sportamongthepoorlycoupledmolecules.TheestimatedintermolecularoverlapintegralsforeachCompound址Soimply血atthelni11im如10veTlapintegralof~10-2evisrequiredfordetectionofthe6eld・effectcharactedsdcs.

β)(a)Ka口_H.E.che机λdωιr.2004,16,4748.(b)TaM111iya,K.;Kunugi,Y.・ToyosMmaY.;otsubo,T.J'A1ル.chι"1.SOC.2005./27、3605'(C)Takimiya,K.;Kunugi,Y.;Konda,Y.;EI)ara,H';ToyosMma.Y';0仭11bo,T.J.A"1.chι机SOC.20n6./28,3044.(d)Merlo,J.A.;Newman,C.R.;Gerlach,C.P.;KeⅡey,T.W.;MuyTes,D.V.;Frilz,

F.;Frisbie,C.D.J.A刀1.che1π.SOC.2005,/27,S.E.;Toney,3997.(e)P釘Mn,S.R.;Anthony,J.E.;KUO,C.・C.;Jackson,T.N.J.A子11.chι挽.SOC.2005,/27,4986.(Dxiao,K.;Liu,Y.;Qi,T.;

Zha口g,W.;wang,F.;Gao,J.;Qiu,W.;Ma,Y.;cui,G.;chen,S.;Zhan,X.;YU,G.;Qin,J.;HU,W.;zhu,D.J.A所、chι"1.SOC.2005,/27,B2幻.fg)Ando,S.;Murakami,R.;Nishida,J.・1.;Tada,H.;Inoue,Y.;Tokito,S.;Yarnashita,Y.ノ.A1π.chι111.SOC.2005,/27、14996.

(4)Lin,Y.Y.;Gundlach,D'J.;Nelson,S.F.;1ackson,T.N.1ΞEEE1ιCtr011DιυiCι1ιπ.1997,/8,87.

(5)Ha"k,M.;Klauk,H.;zschiesch即3,U.;SC11mid,G.;ponomaTenko,S.;Kirchmeyer,S.weber,訊1.AdιJ.λずater.2003,15,917.

(6)(a)sundat,V.C.;zaumsejl,J.;podzorov,V.;Men釘d,E.;W"1ett,L.;someya,T.;Gershenson,M.E';Rogers,J.sciιπιι2004,303,

1644.(b)Takeya,J.;Y卸agishi,M.;丁ominati,Y.;Hirahara,R.;Naka2awa,Y.;NishikaW丑,T.;Kawase.T.;shimoda,T.;ogawa,SAPPI.ph)智.blt.2007,90,102】20.(C)Jurchescu,0.D.;popincluc、M.・va11WeesB.J.;palstra,T.T.M.Adι,.ua1ιr.2007,19,688.

Orga11icsemiconductorsplaythemostessentialpartas

acdvelayersinorga11iC6eld・e丘ect住飢Sistors(OFETS).They

havebeeni11tensivelySωdiedrecendybecauseoftheir山lique

adV釦tagesagainstconvention址Silicon-basedFETS,includ・Ifb'titlvdh'址

aexibiⅡty.1Duringthepastdecade,signi丘C釦tprogresshasbeenachievedfortheoFETsinbothmate貞alsdeve]opment

釦dadvancedfablicationtech11iquestowardtheindustlial

applicaιion.-knongthem,alargealnountofeffolthasbeendevotedtodevelopinssupedorp-typeorga11icsemiconduc-

Introduction

*Towhomc0丘espondenceshouldbeaddtessed.M.A.:phone、+8148-467ー9412;f飢,+8148-467・斗661;e・1mil:mashi2awa@dken.jp.J.T.:ph011e,+81・66850-5398;fax,+81-6-6850-5398;e・mail,takeya@chem.sci.osaka・U.且C.jp'

'condensedMolecularMatetialsLabotatoryキCurrentaddress:DeparrmentoforoanicandpolymedcMateti且IS,Tokyo

InSⅡ田teofTeclm010gy,ユ・12-10・okayama,Meguro・k11152-8552,J且P丑n.phone:+81-3.5734,2426.Fax:+81-3-5734-2876.E・m且il:丑ShiZ且W且.m.丑a@m.titech

4883

j

acJP.,MSRL

"osak且Uηive丁Sity.(1)(a)Dimitrakopoulos,C.D.;Mascaro,D.J.Adu.λlale武2002,/4,99

(b)Gamier,F.;Hajlaoui,R.;YasS丑r,A.;srivaslava,P.sciι"ιι1994,265,1684.(C)Bao,Z,Adu.Uα1ιr.2000,/2,227.(d)HOTowitz,GUaler.chι1?1.1999,9,2021.(e)Horowitz,G.Adι,.Uα1ιr.1998,10,365.(今ln7hiπ・FihπTraπSistors;Kagan,C.R.,Andry,P.,Eds.;MatcelDekker:NewYOTk.2003;P37フ.(g)Btiseno,A.L.;Tseng,R.J.;Llng,M.・M.;Fa】cao,E.H.L,;Yan旦,Y';WⅡdl,F';B丑0,ZAdlj.uatιr.2006./8,2320

(2)(a)Facchet6,A.;Mushtush,M.;Katz,H.E.;Marks,T.J.Adu.λずαtιr.2003,15,33.(b)M田飢fant,P.R.1...;Dimj力'akopoulos,C.D.'Gelorme,J.D.;Kosbar,L.L.;.血am,T.0.APPI.アhys.ιιtl.2002,80,25】フ.(C)Babel,A.;Jenekhe,S.A.Adu.uatιア.2002.145,371(d)FacchetTi、A.;Deng,Y.;wang,A.;Koide,Y.;slrringhaus,H.;Marks,T.J.;Frie11d、R.H.A,18ιW.C1姑ln.,1πt.Ξd'2000,39,4547(e)Facchetti,A.;watlg,A.;MaTks,丁.J.;siπinghaus,H.;Deng,Y.;Friend,R.H.poly1π.uatel・.sci.Ξhg.2000,83,290.(f)Ka伐,H.E.;JohTlson,J.;Lovinget,A.J.;1'1,W.J.A挽.chιhl.SOC.2000,j22,フ787

torswithhiohcatrie里mobilitieswhen加Corporatedinthe

FETdevices.3AmobjHtyvalueashighaSμ=1.5Cm2V-1S-isacMevedforpen仏Cenepolyclysta11ine伽n61msonChe血Ca11ymodi6edsurfacesofsioysisubstrates,4andμ

1.1Cm2V-1 isre凪izedforalkyl・attachedoligoth・

iopheneth加・6hndevices.5Fortecentlydevelopedsingle-ClystaloFETS,theNghestmobilityforr口brenecrystalsreachesmoreth即~30cm-V-1S-1,WMchs{ⅡPasseseventhatofalnotphoussiliconFETS.6Formaterialdesi部toimprove血edevicepedorm釦Ce,

itiscruci址toelucidatemecha11ismstorelate血e血Croscopic

molecularatra11gementt0血emacroscopicelectr011icchargetta11Sportdemonstratedin血eFETperforma11Ce.TomakeUseofthe6111Capabilityoftheorg釦iccompounds,血e

1S

4884 Chel".Uωer.,V01.20,NO.15,2008

Schemel.chelmcalstructuresofpyreneDerlva註Ves

艦^'・.,j.ー.ー.島,11..、血UI'＼

OPⅡ加ZedmolecularpacMngisindispensable.However,1ittle

isreportedonsuchfundamentaltopicssofar,despite小e

recentdevelopmenlofnovelmolecu】esarldl'abHcalion

Processes.ー'3T11iswouldbebccauseextrinsjce什ectsfromgrainboundariesoftenobscuretheintdnsiccatder廿釦Spolt

PropeπiesofthepolycrystaⅡineorganicmaterialsinthe

Comm0ηlystudied小in・田mFETS.onthe0小erhand,sinole・

CrystaloFETsaresuitableforstudiesontherelevanceof

themolecularpacMnowi血Outcomplicationsduetothegrain

m0甲h010gies.Moreover,useof小esingle・crystal-based

transistorsexpa11dsthepossibiliwofdetecdDgthe6eldeffect

evenforlow・mobilityse加ConductorswMchwouldnot

Operateindlepolyclyst飢linestate.

In血isstudy,weusedmoleculeswiththepyrenecore

becausepedphetalmodi6Cationsca11beeasilyaccessible.

AnotheradV釦tageofthepyrenededvativesiS山atthe

Cryslalsarefavorablygownintotheshapeoft11inplatelets,

SothattheirmolecularlyaatsurfaceisUⅡlizedtoformaatinterfacessuitablefortheFETchannelsasat仏Chedtothe

gate・jnsulatinglayer.1naddition,thepyrenecoreisalsoa

Usefulelectrolunlinescent(EL)unitusedinorga11jclight・

enli山ngFETS,7WhoseELcharactedsticsC釦bemodi五edbyperjpheralmodi6Cations.weusedthethjenylmoietyas

伽epedpheralgroups(schemeD,expectingmodi6ed

elecbon・donatingatldELpropeniesofpyrenes,andvarious

molecularpackingsinthecrystals.1nthisarticle,wereport

thesynthesis,solutionproperιies(redox,absorP註on,釦d

e血Ssion),andcryst址StNctutesofpytenededvatives(t訊10

isofomlsofle廿alhienylpyrene18andlwoisolnersofdjthienylpyrcnC2)即dtheFETperfonnatlcebasedontheir

Singlccrystals.wecomparetheFETperforma11Cesoftwo

isoformsoroftwoisomerswithequivalentredoxpotentials,

Sothat血einvolvementofmolecularpacMngca11beexalninedinthesalneconditions.

S S /S ノノ

OnaS11imazU4121,a11demissionspectrawerec011ectedona

ShimazU4123.cycljcvoltalm】etty(CV)waspetfomledwithanALselectrochemistryanalyzetmode1610A.ThemeasU工ementwasPedormedinbenzonitrilecontaiDin8adonormolecule(02mM)andte壮a・11・butylamm011iumhexa丑Uorophosphate(0.1M)asaSUPP0πin3electrolyteusingagrassycarbonworkin名electrode,Platinumcounterelecuode,atldAg/AgN03teferenceeleC註'ode.MSSpectraweteobtainedwitha正OLJMS・SXI02AfolEI・MS.Theme1血gpointsweredeter血nedwj血aY釦acoMpmicromeltinσPointapparatus.Microanalyseswereperfonnedat止eNlicroanalysisCenter、NKEN.

Mate"alsynthesis.Telrathieh)カフ)り'e11el.Toamixtureoftetrabromopyrene(1.og,1.93mlnoDandsodiumcarbonate(1.0g)inl,2、dimethoxye小ane(20mL)andwater(30TnL)wasaddedP田ladiumtetrakisttjph帥ylphosphine(0.082g,0.07mm0りinoneP0丘ion.ThemiXωrewasheatedunderreaux,andasolutionof2・壮lienylbor011icacida.1639.1mmoDin1ユ・dimethoxyethane(20mL)wasaddeddropwise.ThemiXωrewasheatedunderreauxOve加ohtandcooled.Afterremovalofthesolvent,theresulting

resjduewasextractedwithbenzeneatld61tered小roughcolulnnChromatography(silicage1小enzene)toaffordlasapaleye110WSoljd(0.25g,25%).slowevaporaⅡonofthecSユーhexa11e(1:1,V/V)solutionaDdthephysicalvaportra船Port(PVT)method(detailedconditionsaredescdbedin廿)eFETcharactensdcssecuon)Ofloaveyel】owneed】essuitableforx・rayanalysis.se]ectda仏ateidentiC址tothepreviousreport.8CompoundS2and3WerePreparedsimilaTly.

Dilhie,1ツ1Pyl'eπε2.Quanι川eswereasf0110WS:pa】1a小Umtel・rakistdphenylphospMne(0.041g,0.04n血OD,dibromopyrene(034呂,094mmoD,and2・thyenylboronicacid(03632.8脚noD.ColumnC11romatography(silicagevcS2)gaveapaleye110訊Isolidasa111ixtureofl,6・釦dl,8-isomers(71俣)).Forx-rayanalysis,SlowevaporationofthecS2-hexa!1ea:1、V/V)S0111Uonof2gavePaleye110wneedlesofl,8-isomer(cis・2),whereast11epvTme血odaffordedpaleye110wneedlesofl,6-isomer(1ra段S・2).MP113-1160C.1HNMR(CDC13):δ723-728(m,6H),8.07-8.21(m,6H),8.49-8.52(m,2H).MS(m/Z):366N+).Anal.calcdforC24H14:C,78.65;H,3.85.Found:C,7827;H,395.These

SpectraarefoTmixtureofci'ξ一2al】dlra11S-2.U0丸olhie,1ylpyrιne3.Quantiueswereasf0ⅡOWS:pa11ad加m

tetrakistriphenylphosphine(0.10g,0.09mmoD,m0ηobromopyrene(0.80g,2.84mm01),and2-1hyenylhoronicacid(075g59mm01).Flashcolumnchromatography(silicagevcS2)3avewhitesolid3(9易).MP=80-83゜C.】HNMR(CDC11):δ727(d,J=3フHZ,IH),738(dd,ノ=22HZ,ノ=1HZ,1H),フ.52(dd,ノ=4.OHZ,

ノ=1HZ,1H),8.00-822(m,8H),8.49(d,J=9.5H21H).MS

("1/Z):284N十).Anal.calcdforCユ0H】ユ:C,84.47;H,425.Found:C,84.25;H,4.25

X.raycrystalstr11CtureAnalysis.crystalstructuresweredetermjnedbysingle-crystalx・Taydi什ractionda仏.Measurem引北SWeremadeonaRioakU爪ISCMercuryccDsystemwithgraphite・monochromatizedMOKaradiation(2μく55゜).struCωreswereSolvedbydirectmethods(SIR97).stmC加reswerere介nedby小efu"・T"a伽X】e鮎t・sqU丑resprocedurebyapplyingaηisotropjctem・Pcralurcfadorsl'oraHnon・hydrogcnaloms.TheposilionsofιhehydTogCηalomsworecalculaιed.Thcqualilyofιhere6nedStNCNresshouldbealmostthesameforthepresentsalnplessince

theRvaluesareaboutl0易;therefore,thedifferenceofFET

Petforma11Cewouldcomefromdi丘erentmolecularpackings.ThePresentcrystalqualiwissU伍Cientwi血Ouresti11】ationofoverlap血teoralsincomparizonofFETperformance.Thesevalueswould

3

AshizaWαιlal.

ExperimenねIsection

GeneralRemark.AⅡChe加Calsatldsolventswereofreaoent

σradeunlessotherwiseindicated.A11reactionswerecatriedout

Underanal'oona血Osphere.THFwaspuri6edby'stiⅡationfromSodiumbenzophenonekethylunderargonpdortouse.pyrenear】dmonobromopyrenewerepurchasedfromTokyocaseilndustTydcD,atldtetrabromopyN口e4帥ddibromopytene5Werepreparedaccordinotopreviousrep0丘S.9'1゜NMRspectrawereobtail)edwithaJEOLJNM、AL30ospectrometer.1.Ⅳ一visspecttawerec0Ⅱected

(フ)oyamada,T.;uchiuzou、H.;01こU,Y.;shimoji,N.;Ma船Ushige,K.;Sasabe,H.;Adachi,C.ノ.APPI.ph),S.2005,98,074506-】.

(8)zhang,H.;訊lang,Y.;shao,K.;[iu,Y、;chen,S.;QiⅡ,W.;sun,X.;Qi,T.;Ma,Y.;YU,G.;SU,Z.;zhu,D.chε"1.CO"1抗U月.2006,755

(9)V011ma11n,H.:Becker,H.;cotre11,M.;SⅡeeck,H.ノ弘C11ιfιiebi8SA加C1詰1".1937,53/,1

(10)(a)Grimshaw,J.;Trocha-Grimshaw,J.J.C五e所.SOC.,perki町1972,ノ,1622.(b)Minabe,M.;Takeshige.S.;soeda,Y.;KimuTa,T.;Tsub0仏,M.BU11.chι"1.snc.JPπ.1994,67,172

Si見ξleC1ツS1αISQi'7hiι11〕,1・S1ι力StilU1ιd,)'rιnιS

explainthedifferenceofFETpedonnancebasedonmoleCⅡlarPackinosdiscussedinthemaintext.cryst址10graP11icdatahave

beendepositedattheccDC,12U11ionRoad,calnbridoecB21EZ,U.K.,a11dcopiesca11beobtainedonlequest,fteeofcharge,byquotin0仕)epublicationcitationa11ddeposiⅡonnumbersccDC・668229-668232

FETcharacteristics.Thesinole・crystalFETswereprepated

bystandardmethodS伽atwereappliedtocopperph血alocyanineandnlbreneC工ystaltr抑Sistors.11Partof血esinglecrystalsofthePyrene・bagedcompoundsweregrownbyhorizontalphysjcalvapor壮a11SP0π(PVT)inagtlealnofargon旦as;12Usingatwo-zoneωben】mace,powdersofsyn小esi2edmate丘alsweresublimedin止eUpstreamh0ミZone.ThesublimedmoleculeS訊,erecardedbyanaTgoTlstTeamandcrystaⅡizeinthedownstreamcoldzoneof小efurnace.Thetemperaturesofpowderandcrystalzoneswerekept

typjca11yfor12hat310andat280゜C,respectively.TherestweregrownfromsolutioninthecS2-hexanea:1,V/V)solutionafterrecrysta11izingNjcetoimprovecrystalquality.weselecredtMnCwstalswithawpiC址仕ljchlessof紅Ound50onm.The陀TS如C加Tewascomposedbyei血erat仏C11ingthectyS仇Isonsubstrates

WithpolymeriC3ateinsulators[PO】y(vinylphen01)}ordepoS批ngPalyleηet11roughpolymeri2ationatroomtemperaωre.solafhon1260and】296impedaTlceanalyzerswereusedtodete血inetheCapacit即CeofrhegatedieleC訂icinsulators、圦『enotet11atthetwotechniqueswereestablishedusingr口brenesinglecrystals,givingequa11y11ighvaluesofmobilityexceedinglocm一八TS.The廿ansislorPerformancesweremeasuTedusingtwosourcemeasureunils

(S入4US)equippedinanAgilentTechη010gyE5270semiconduclor

Pat町leteTanaly2er;oneapplieS3atevoltage飢dthe0血erapplies

drainvoltage,a11dtheymeasuredraincurre址,sothat血eC卸iel

ConduC廿ViW血仕lese血Condudorch田111elismeasuredasafunCⅡonOftheapPⅡedgatevoltage

Scheme2.synthesisofThienyl.substi加tedpyrenes

ぜ、,ニ。・礁'."-U^i尋1゛1....・・・。。゛^

Che1記.ualer.,V01.20,NO.15,2008488S

4

Synthesis,Electrochemistry,andopticalproperties.

ThesynthesesofthepresentcompoundsareoudinedinScheme2.synthesisofte虻athienylpyrenelwasreported

inref8.Thestarringtetrabromopyrene4anddibromopyre乃e5Wa'epreparedinasimilarwaytothatdescribedinprevjousreports.9'1゜Thepresenlcompoundsl,2,a11d3WerepreparedbyoTdinarysuzukicouplingreactions01'bromo-subsliιUted

Pyrene4,5,and6With2・thienylb01'onicadd,respectively.Dibromopyrene5,whichisalmostamixtureofl,6・and

】,8・dibromopyrene(rati0久ご5:4),1゜wasusedtoyielda血Xt山eof16・飢dl,8・isomersof2.Toourhlowledge,

didlienylpyrene2a11dmonotNenylpyrene3Werepreparedforthe五rsttime.

Redoxproper廿esobtainedbycyclicvoltalr帥e町(CV),{Jvabs0中tiona11de血Ssjonmaximumvaluesfor山epresentCompoundsaresummarizedinTableltogetherwiththe

Correspondingdataforpyreneforcomparison.on血ecvmeasurement,pyreneand3Showedonequasi-reversibleOxidationwavewNlela11d2Showedtwooxidationwaves.

Theexistenceofthesecondstepinla11d2isascdbableto

ReSⅡltsandDisCⅡSsions

(HO)2B

5

S

＼/

Pd(pph3)4,Na2C03

DME,H20

＼

.,...申

S

/S

;'令':..

S

Tablel.Red0叉゜合ndpbotophy'C合1ιProperaes

CompoundsE1恢(V)E2悼(V)λ。獣,御(nm)λom、,脚(nmy4664040.87 】.121

が 434096 3721.12

4053491.143

3933381.68Pyrene

゜versusAg/AgN03inphcNwi伽0.1M11・BIUNPF6,gassycarbonWorkinge】eC廿odesca"rateloomvs-1.hMeaSⅡredinlo-5MCHC】きSOIU60ns.'E叉Citedat315nmforl,ユ93Πmfor2,278nmfor3、and

337nmforpyre口e.dAmiXωreofl,6・a11dl,8・isomeTsof2.1nourmeasurementseωP.e訂'orsincvmeasurem己ntarewi血ino.0IV

/

2

(HO)2B

6

Pd(pph3)4、Na2C03

DME,H20

S

＼/

8

4

6

5

7

2

/

S

al)(a)podzorov,V.;hd址OV,V.M.;Gershenson,M.E.APPI.phys.hn2003,82,1739.(b)Takeya,」.;Goldmann,C.;Haas,S.;pemS註Ch,K'P.;Ketterer.B.;Ba目10gg,B.J.APPI.phys.2003,94,5800.(C)deBoer、R.W.1.;Klapwijk,T.M.;Morpurgo,A.F.APPI.phys.1ιπ2003.83,4345.(d)Yalnada,κ.;Takeya,J.;shigeto,K.;Tsukagoshi,K.;Aoyagj,Y.;1Wasa,Y.A171.phys.1ι11.2006,88,122110

(12)KIOC,ch.;simP辻IS,P.G.;siegrist,T.;1"audise.A.ノ.C,),.gt.GroW所1997,1×2,416

thewidelyspreadπfralneworkoverpedpheralt11ienylgroups.1nP田ticular,sincea加Xtureofl,6・atldl,8-isomersOf2Showsnodistinctseparationof小e6rstoxidationstep,小e6rstoxidationpotentialsofl,6・釦dl,8・isomersof2Shouldbealmostthesalne.TNsisalsocon6mledby血e

extendedHiickelcalculationbasedonx-raystructute

analysiswhichindicatesalmostthesalneHOMolevel.The丘rstoxidationpotenⅡaldecreasesintheorderpyrene>3>2>1,血dicatinotheelectron・donorabilityisenha11Ced

byintroduC杜onof山e血ienylgroup.Asexpected,thebt'd'mfseriesofthienl-

SubstitutedpyrenesareredshiftedwithincreasingnumberOfthienylgroups.Thesefactswould伽dicatethatthethienylgroupreducestheenergyseparationbetweenthehighestOccupiedmolecularorbital(HOMO)andthel0訊,estunoc-Cupiedmolecularorbital(LUMO)owin今totheextendedπConjugation.

CrystalstNCωresofpyreneDedvatives.singlecryS仇ISOfthepyrenederivariveswereob仇inedbytwodiffereηtProcesses;oneissl0訊levaporalionfromanorga11icsolulion,a11d小e0山erisphysicalvaportransp0札(PVT).X・raysi打gle・Crystalstructureanalyseswerecarricdoutforlatld2.Dependingoncrysta11izationme小ods,1a仟ordedentirelydifferentwpesofcrystals:amonoclinicsystemwiththe

一ノ

.甲

S

゛、,

B

4886 C11ι,π.λずαter.,V01.20,NO.15,2008

ChemiC且lforlnula

fW

C010T肋dshape

CTystsyst

Spacegroup

α(A)占(入)ι(A)β(deg)V(入3)Z

DO"kd(gcm-、')T(K)R/RWreansused

1丑

CきユH18S4530.73

ye110wneedlemoTloclinic

P2」hl

3948(2)11.007(6)2736(1)90278(9)1188(1)2

1.158

297

0.H63/03397

2711q>2.00の

SpacegoupP21hlbyslowevaporation(1a)andamonoclinic

SystemwiththespacegroupP2ノπ(1b)bythepvTmethod.

Differentialscanningcalorimetry(DSC)measurementofl

exhibitedonlyonepeak,suggesting山atldoesnothave

enanthiotropiccrystalpolym0ゆhism.Thesestructuresare

differentfromthatrepor[edprevious】y(monoclinic,space

groupC2/C,a=20.664(4)A,h=12.BO(2)入,C14363(3)A,β=92.894(3)゜,V=3565.4al)人3,Z=8).8Amixtureof16・飢d18・isometsof2affordedsinole

Crystalssuitableforx-raystructuteanalysis:】,8・isomer

(abbreviatedasds・2)byslowevaporaⅡonandl,6-isomer

(abbrevialedaS力'aπS・2)bylhepvTmelhod.However,we

COU】dnotobtainsinglecrystalsof3forx-raystructure

analysis.1nthissection,werep0πthemolecularandcrystal

Structuresofthefou『CTystals.1naⅡSamples,molecules

ContainaaatpyrenecorecolmectedtotwistedtMenyldngs.

Crysta110graphicdataforcompoundsla,1b,cis-2,a11dIr4πS・2areⅡStedinTable2.

Tetrathienylpyrene:1a.nemolecu】ar帥dcryst址Struc-

ωresoflacrystalHzedfromacarbondisU16de-hexarle

SolutionareshowninFiσUrel.1acrysta11izedina

monoclirⅡCsystemwith血espacegroupP21hl.ThemoleculeislocatedonaTlinversioncenter.Theconf0伽ationsoft訊,0

Crysta110graphica11yindependentthieny】dngsaretwisted

aroundtheC2-C9andC6-CBbondsintheopposite

directi0那.Thetorsjona11glesbetweenthepedpheralthienyl

dngsal】dthepyrenepla11eare42.1(2)゜fortheC2-C9bond帥d41.フ(2)゜forlheC6-C13bond(Figurela).AsshownjnFjaurelba11dlc,themolecu】esmakeuniformstacks

alongtheaaxisandshowcofacjaloverlapbetweenadjacent

molecules;theiηterplanardistancebetweenthepyrenecores

iS3.57(1)A.Theneighbodngstacksarerelatedtoeachotherbythe2・foldscrewsymmetryalong血ebaxis.Therearenoremarkableinwrstackshortcontactswjthinthesumof

theva11der圦Taalsradii.Therefore,thisstrⅡCtureseemsto

beone-dimensional,a11dsizableintermolecularoverlapis

expectedonlyalongtheα飢is.Theintermolecularoverlap

integrals,S,betweentheHOMobasedontheextendedHilckelmethodarecalculatedtobeS駕S彫2.5×10-4

(enetgydispersionofthepresentcompoundsisshownin

FiguresD.13Thesesvaluesresultinnosigni6Ca11t6elde丘ectforthesingleclystalofla(vide血fra).

t0

Table2.cryso

1b

C32H】8S4530.73

ye110wneedlemo"ocli"ic

P2/h

14.192(14)6.B5(5)15912(17)116.158(16)

1243(2)

'CData

Ci$・2

Cユ4H14Sユ366.49

Paleye110wneedlemonoclinic

P21/h

11.971(4)394(D35.70(D90.454(3)1685.4(9)4

1.444

297

0.086ν0.2644

3838(1>2.00σ)

1.417

297

0.1144/0.2415

2833q>2.00σ)

Ash1之awaetal

11口ns・2

CリH14S2366.49

Paleye110wneedlOrthorhombic

Pらιa

フ.88(D11.44(2)18.11(3)

Tetrathienylpyrene:1b.Thecrystaloflbbelongst0血e

monoclinicsystemwjth血espacegroupP2/n.Fi旦Ure2Showsmoleculara11dcrystalsnucturesoflb.Asinla,dlemoleculeislocatedonaninversioncenter.Theconforma-

tionsoftwocrysta110graphjca11yindependentthienyldngsConnectedtoC2a11dC6atomsaにeverysi血lattothose加

Ia(Figure2a);小etorsi011anglesbetwNn小ethienylrings

andthepyrenecoreare47.5(5)゜fortheC2-C9bonda11d

1631.3(3)4

1.492

297

0.1199/02969

1871q>2.00の

a

令

..".."

CB

.0

C,5

t命C1

b)

a3)M06,T.;Kobay鮎1ゞ,A.;S鮎aki,Y.;KobayasM,H.;saito,G.;1nokuchi,H.BU11.chε1π.snc.J'pn.玉984,57,627

C

S2

C7

C1

C9

C,ユ

51

CI,

S1

C11 JCI0

Q,

冬

C1

t

C"

C,B

'角

CI'

円『コ

S2

^

゛,

卑ψ,

C)

P

'

b

戈詠〆、'心、ξt1文。.、、ゞ穿ご'密'/5-'。。'文成交ゞ念゜。.、_泳ゞ穿ご'密'/5{。。'文一丁、工1ヨj海1一之j,空巨^江..ざ'1^、壕1・、、111ヨj海¥。'、

b闇

0

a

f1考nrel.cryS仏Islructuresof1丑.(a)MolecularS如Cture,(b)projcCⅡonOnlbebcP1釦e(1eft)atldoverlappingmode価帥1),arld(C)vjewalongthe6axis.

(Nerlappin9mode

う一

珍C'、、

一ノス、筏yユ,エ

>

R玉C

亀

光争こ

違こ.

メ、

0メニ

肇門

ヘ

魯r

Si"81eC乃,stalSげアhien),1・SUみSlituledp),1'ιπιS

a

CI0

C71?

S, C2

C,

S2

C3

0,'倉

C6

C8

C13

C

CM

C15

(b)

.

C11-゛^無、.→励恐C,2そ、

魯

CI0

0

禎ン

,一

ρ.

,喫、

巻SO・'

0

ノ

ヨ

$,

,倉゜"

、ー',奉^C伯,'、

Chι机.Uα1ιr.,V01.20,NO.15,20084887

釦dlhepeljpher田山iophenedngs.ThemoleculeS血lbfonnConductionpa由WaysintheみCplane.

D難hienylpyrene:cis・2.cis・2Wascrysta11izedinamono・CⅡ11icsystemwiththespacegroupP21hlbyslowevapoTationfromacS2-heX田lesolution.Themoleculara11dcrystal

Structuresofcis-2areshowninFigure3.AsshowninFigure

3b,themoleculesofcis・2makeunifotmstacksalongtheb

axis;theinterplanardista11Cebetween小epyrenecoresis3.58(1)人.Thcrcisnosidc・by・sidcintcrmolccularcontactinthestructure.Therefore,cis-2hasoverlapintegralsofsp

2.5×10-3ands=フ.O×10-5,indicatingtheone・dimensionalnaturealong血e6axis.sincethesingle-crystaldevicemadeofthiscompoundalsoworksasanFET,itis

】ikelythattheoverlapspisl'esponsiblefor小eFETopeTation(videi11tia).

D赴hienylpyrene:かαπS・2.ThepvTmethodgavesingleCrystalsofthel,6・isomerof2(1rαπS・2)be】on部n3toanOrthorhombicsystemwi小thespacegroupPみCa.Thcmoleculara11dcrystalsuuC山resof訂'α11S-2areshowninFigure4.Theclo/slandC13/S2atomsofthethienylnn旦aredisordered(Figure4a).1n血ecryst址St皿CtureoftrαπS・2thereisnodistinctstack,a11dtheoverlapintegralsintra11S-2

ares=2.6×10-4,SI=1.4×10-3Sq2=1'5×10-3,andS3=22×104.TheoverlapsqlisassociatedwithCH-・scon仏Ctsshortert11anthevanderwaalsdista11Ce

be[weenthepyrenecoresa11dthepeTipheraltMophener血gs,andtheoverlapsq2ComesfromoverlapsbetwNnnei冬hbor-ingthiophenerings.Among伽epositionaldisorderedatomsOfclo/S2andsvcB(Figure4a),theoccuP釦Cyofsla11dCloatomsislarger血anthatofS2arldcBatoms.Thereforesla11dcloatomsareelnployedin血ecalculationOfHOMO.

FETchaMcteristics.Toexalrline血eFETpelfolma11Ces

Oft11eabovecompounds,weemployed仕lesingle・cryS仏IFETtechrliquethathasbeenrecendydeveloped.HAlthoughweattemptedcrystalgroW山,山esinglecryS伽of3S山tablefor小eFETmeasurementandx-raystr日Ctureanalysiswasnot

Obtained.Figure5ashowsthetopviewofatypiC址Single・CrystaldeviceforlbgrownbythepvTtechnique.AplateletOfaιhinclystaloflbwilhalhichlessofapproxima【ely50onmiselectrostatica11ν1αm加αtedtothesubstratewhere

Sourcea11ddrainelectrodesarealreadyimplemented.TheChanne11eno"thιandwjdthwarC150andlo0μm,

respectively.1n小einsetofFigure5athet11intransparentCrystaliselongatedt0小eみaxisdirecuonarldat仏ChedtotwogoldelectrodeselongatedinthedirectionoftheaaxisOf山ecrystal.Theoverlappedre8ionsworkassourceanddrainelectrodes.訊TenotethatthehighestmobiⅡtyof40Cm2八7SisaC11ievedforrubrenesinσlecrystals,fonninggoodOhlniccon仇Ctsatthesourcea11ddraineleC廿odes.The

ditectionofthechanne11engthissetpara11eltotheclystal-10graphicdirectionwith血elargestorbitaloverlapforaⅡ小emeasureddevices:theaaxisforla,the6axisforlb,

小e6飢isforcis-2,al】dtheaaxisl'orかα11S・2.Thedil'ecljon

Ofthesin旦lecrystalwascon五血edbyx-raystruct山e釦alysis.Thegateinsulatorsusedwerepoly(vinylphenoDforlaa11dlbarldforparylenecis・2andlr伽S・2,respectively.PI0杜edinHgure5aaretransfercharactedsticsofthe

Single・CTystaldevicesofthetwotetrathielylisof0柳Slaand

、

(C)

〆

イ

.

C14

C

.

6

r

七&

、入＼

C

.

0

ノ<

OV引lappin9r"ode

0、ヘ

0

W令r 0

9

0一

)゛

、

0

.、

『'、

Fi名Ⅱre2.cryslalSιruCιUreoflh.(a)MO}ecularslNclure,(b)projeCιionOn血eacp】aDeaeft)andoverlappingmode(dghu,and(C)viewalongthe

凧

aaxls

q1

ノ

Pし

0

44.9(5)゜fordleC6-CBbond.Althoughtheinversion

Operationinlaa11dlbproducesan卸alog011Smolecular

geometry(planarpyrenecorea11dtwistedthienylrin容S),it

isnoteworrhyt11ataS輩ghtconfonnational(torsionangle)

di丘erencebetweenthe壮lienylrinosa11dthepyrenecore

Wouldcome負'omthemolecularpacking.AsshowninFigure

2ba打d2C,themoleculesoflbuniformlystackalongtheb

饌iswithanintclp】anardistancebctwcenthcpyrcnccores

Of4.09(3)人'Theovetlapinle今ralsaresp=13×10-3,sql1.1×10-3afldSユ=4.5×10-5,whjcharesigni6Carldy

Iargerthan小Oseinla.sinlbislorderofma今nit11deIargerthanthoseinladespitethelarge加terplanardistance

inlbcomparedwiththatinla.Thispointsoutthat

in比rmoleculatπ一πinteraC壮onsdependnotonlyon小ein証うrmolecU1紅diS仏ncebutalsoon仕leintermolecular

HOMO-HOMophaserelation.1nthestructⅡre,仕lese

OvedapswouldbeassociatedwithcH-.scon仇Ctsshoder

thanthevanderwaalsdistancebetweenthepyreηecores

d

^

七、、ノ

5

0<、

,^

易.゛

1コ

'鸞

.、.

゛、

rげ

1.

4888 Chel".uater.,V01.20,NO.15,2008

a

S2C16

C15

C6

C

b)

C,

C5C4

^

C1

C20

C7

C6

12

S,

10

C喝1

C.

C忌

'すCI.

,...

0亀.剛

、to,_^、.、_゜

^....

S,

円'

(C)

C2 C,

C

一ゴ

、

一田趨、つ bq

F電Ure3.cwst田St川Ct山eofcis・2.(a)MoleC田arS加Ct山e,(b)PTojectioDOntheacp】a11e(1e丘)andoveT】appingmode(tight),(C)viewa】0τ13thea

゛

^

Whereha11dkBarepla11k'sconsta11ta11dBoltzmatln'S

Consta11t,respectively.NodDgthatthecomponentmoleculesOfthetwocrystalsareexactlythesame,there()rganizationenergyisidenticalbetweenthetwoisoformcrystals.Thereforetheessentialdi什erenceinmobilityisattributed

tothevadationinthemolecularpackingofthecrystals.ASdiscussedabove,crysta110graphicanalysisshowsintermo・Iecularoverlapsofaboutlo-3forthelbcrystal,whereasthevalueofthep"maryoverlapintegralisoneorderofmagniωdesma11erforthelacrysta】.Therefore,itcanbeinferredfromeqlthatthedifferenceinscancausethe価ffel'ence加小etransistorpelfomlal〕cesbetweenthetwoisof01了11S.

Ncxt,wecomparcthe6e】d-e丘ectperformal】ccsfortheCrystalsofisomercompoundscis-2andtrαπS-2.Theset工刃0moleculeshave血eS町lenumberof小et11ienylgroupS祉ld

冒

axls

0

0.

_4π2.S2二L-Tヲ玩*,応

Ib.Thedeviceoflbshowsapparenlp・1ype6eld-effecl

Charac{erislicsasnegalivegalev011agevcisapplied;the

drainculrentlD(dHve11bythedrainvoltagevD)incrcases

WithmobileholesacC口mulatedatthesurfaceofthesingle

Crystal.TheFETmobilityisestimatedtobeμ知0.02Cm2ハノSusin合thesta11dardequaⅡonμ=UW.1/(CVD).d11)/dvG,Wherec,isthecapaci御Iceof血eoate血Sulator.Typical

OU中UtcharacteriSⅡCsshowninFigure5bareobtainedfor

血esarnedeviceofthelbcrystal,givingalmost小esalne

Valueofsaωrationmobi1武y.wenote小atthepresenteddata

areofthedevicewiththehighestmobilityalnong6Ve

S釦Iples.Exceptfor廿leonewj仕latlapparendybadly

Ialninatedclystala11仕leotherdevicesshowed6eldeffectWithmobilitiesin山eranσeofo.005-0.02Cm2八7SinwMch

thedistributioncouldberelatedt0血auencesofintedaci址

住apsundemeaththe伽ncrystals.

Ontheotherh釦d,noneoft11reedevjcesbasedonsingle

Crystalsof小esamecompoundlashowanyindicationof

the6eldeffect.1nourseωP,itme飢Sthat小emobilityvalue

islessthan~10-5Cm2八IS,ifarly.Evenwiththehighestmobilityo.02Cm2八7Soflbcrystaldevicesitisdif6Culttoassumeb釦dtransportbecausethemeanfrNpathisestimatedroughly20rdersofmagniωdeshorterthanthetypicalmoleculardistance.(weindeedexperjenced小atthemobiHtydecreasedatacolderatmosphedctemperature.)

Therefore,寸leCω丁ierbal】sportmechanismismostljkelyduetohopping.Re3ardingthewe11・hl0吻Ise血ClassicalMarcus

小eory,1heraleforlhecarderhoppjngkisdescribedby

representativeoverlapintegralsa11dthereorg飢ization

CnergyμWhichreferencesgeomctricrelaxationofthe

Chargedmolecules;

゛.亀

OY引恰Ppingmode

Ashizawae1α1

n芸Ⅱre4.cryS仏IstruC加reoflrah工一2.(a)MolecularSιruct山巳,CI0/SIrepresen認止巳Positionaldisorder,(b)projectionon仕leacplane,a11d(C)Projectionon血eaらPla11e

0.

.ι

^

0

.一

(刃

(1)

a

"C12

C9131S,CI

CI0IS2

C2

C3

C5

C'

(b)

7

C,2

C"

C,

ゾ

Sξ蔀".X

C9

C1αSI

'

(C)

、".途

゛0,C1

q20.

CI0ISIC12

a

武＼゜

a

円'

、

1、b

才、。』ノ气、ー

『>、、^

q3

P

6C

C

mC

,令

2

4

R(.一、

)、

L

0

Smξlecl)1St41SQI'Thieπ),1・S1ιみSιilNiedp),rι,1ιS

(ヨ).

伽世界

印畢所

.15

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.1

.08

.06

凸心.4

C2

0

.10 .5

(b)

0

V(V)

Chι1π.ualer.,V01.20,NO.15,20084889

Wouldberelated.sincethetesultsofthecvmeasurements

indicateastrongerelectron・donorabilityforthetetrathienylCompound(sma11mjsmatchwithAuwork負lnction),alowerSch0ιιkybarl'ietaι小esourceeleclroderesU11Sinahigher

hole・injeCιionrareinlhelbclyslal,providingapossible

reasonforthehi6hercarricrtransportjnthelb.

ThepresentexperimentalsogivesanimplicationfortheIeastelectronicintermolecularcouplingtoprovidetheFET

Operation.witNntheseriesofcrystalsofmolecularcom・Poundsofidenhcalconjugatedorbitalsofpyrene,those訊lithOverlapintegralsontheorderoflo-3ShowsapparentFETChatacteristics,even壮10ughthedi丘erentextentofconuibu・

tionofinterfacetrapscausesthevadation血mobilityvalues.Ontheotherha11d,noneofthesingle・cryst址丘ansistorsbasedOncompoundswjthintegralssma11ertha1110-4ShowtheCωTiern釦Sport.1tappearS血atthelowerⅡ血tforoFETOperationresidesintherangeofS駕10-4-10-3,whichCorrespondstoa住a11Sfer血tegrali知10-3-10-2ev.S血Cetheenergyscaleisoneordersm址】erth釦山atofroomtemperature,theelectronicsystemcaηηotrealizebandtrarlsportwithoutaweⅡ一de兵nedFermisurface.ont11e0伽erhand,血eoverlapintegralsinthepentacenecrystal]4WidelyUsedinMgh-perf0肋anceFETbothinsinglecrystalal】dtNnmmformareapproximatelylarger血anrhatofthepresentmolecules(intrastack,-1.6and-1.8×10-';interstack,

2.6and-3.8×10-3)al】dshowtwo・dimensjonalnature.AISO,r11brene,whjchshowsthehighestmobjHtyinthefomlfthl-tltr'trhaalmostthesamesizeof

Overlapinte部'als.Thepresentmoleculesal'edi丘erentfromPenlacenejnviewofeleCιronicproperlies.However,山isimpliesthatnotonlymagnitudebutalsodimensionalityoftheintenno】ecularoverlapsarcprcdominantfactorsforCa柞iertraηSportevenifthechannelofFETissetpara11elto山elargestintermolecularoverlap.sincebandtr釦SponistealizedinⅡlesematerials,asrecendyevidencedbyHa11-

e丘ectmeasurementsofrubrenesingle-crystaltransistors,'thesehigh・mobilitysemiconduct0摺areapparentlyina価丘ere址ClassascomparedtotheseHesofpyrenederivatives.Thepresentobservanonindicatesthatt11eoverlapintegrals笹estiⅡHnkedtothecalTiermobilitythroughsuchmecha-

nismsasgivenineql,giV血grisetothe血nimumorbitalOverlapforthe丘eld・e任ectoperaⅡondlatdependsonmo・Iecularreotg釦izalion.

゛.卑冒

5

.

10

..一

巧

.

0

.

1b

^ーー畳

V暑一10

5

.5

4

^

V(V)

CIS・23

2

カヨ廖・2

0

、120追04004080柁0

V_Ⅳ)

玉1晋山e5.(a)TransfercharactedS百Csofthela釦dlb廿ansistors.(b)outputCh紅acteristicsofthela廿即Sistors.(C)Transfercharacteristicsof血ecis・2and力'απS-2

Si加latelectron・donorabilityasindicatedbythecvmeasurementa11dtheextendedHilckelcalculationbuteX11ibit

differentmolecularpackingpatterns.FigⅡre5Cshowsthe

tr飢Sfercharactedsticsofthedevicesofthetwosingle

Ctystals.Theresultsshowthat血ecis-2device訊,orksaS飢

FETwjlhamobilityV址口eoflo-4Cm2八IS.AⅡ山reeds・2devjcesexhibitmobility11igherthano.5×10-4Cm一八TS,Whereasnoneofthetrans-2devicesshoW6elde丘ect.Again,

Wecanatthbutethedi仟erencein血eFETperformanceto

thecrystalpacking;thecis・2Crystalhasorbi仏10verlaplarger

th飢thoseofthetrα11S-2Crystal.wenotethataworkin容

transistorisobtainedforthed北hienylcryS仏Isgrownfrom

asolution,while【hetetrathienylcrystalsgrownbythepvT

methodexhibittheapparentFETperformance.Therefore,themethodofcrystaⅡizationisnotthepredominantfactortodeterminetheFETperformanceintheptesentclystals.

Acomparisonbetweenthecis・2Crystaland小elbcryst田indicatesthatthemobiliwvaluesdifferbytwoordersthoU套h

小eoverlapintegalsareinlhesameorder,suggestingthat

NO-dimensionaloverlapsinlbaremoreeaectiveforcarder

廿anspodtha110ne-dimensionaloverlapsincis-2.Asfor

di仟erentthresholdvoltagesthedi仟erentgateinsulatoTS

.

、

.10

(14)Matthcus,C.C.;D「os,A.B.;Baas,」.;Meetsma,A.;BoerJan,L.;de;palslra,T.T.M.Aclacly工1α110gr.2001,C57,939

(15)(a)Takeya,にTsukagoshi,K.;Aoyagi,Y.;Takenobu,T.;1Wasa,Y/ph.j.APPI.phy.f.2005,46,L1393.(b)podzofov,V.:入4enard,E.;Rogers,j.A.;Gershe打SO0,M.E.phy$.Rευ.1ιπ.2005,95,226601

,5

.15

0.

{C}

.,

V=.60V

ConC1ⅡSion

Ase"esofpyrenederivativeswithperipheralthienylδroupshavebeensynthesizedtostudy6eld・inducedcarrierU釦Sportassemiconductorsinorga11ictransistors.Applica-tionof血eorga11icsin創e・cryst址FETtechniq11ehasrevealedhtrn血't'tt11trialswi小reard

tth11k'.D'tbtweenthe

twoisoformsofte杜athjenylpyrene狐dbetweenthetwoisomersofdithienylpyrenedemonstrate小atla】!gerovet】apinlegralsbetween血eadjacentmoleculesfavortheFET

V1.

、入

=

.

DV

40

b;

;、

t1

30{亘一・ 20

ヨ1

10

0

言)「

生

4890

Performa11Ces.1thast11r11edoutthat血emolecularpacMng

isreleva11tevenin出eabsenceoftheapparentb田〕dⅡansp011

forthepoorlyoverlappedmoleculesandthat仙etransfer

inteotalc"ticalfortheFEToperationisintherangeof

10一え一10-2evforthesehesof山epyrenedelivatives.ThePresentexpetimenthasdemonstratedanadvarlcedeva]uadon

Usingsingle-crystaltransistorsfordesig11ingnewmolecules

towardhigh-perfonnal】ceorganicse血Conductors.

C11e"1.uatιr.,V01.20,NO.15,2008

Acknowled響ment.we血抑kDr.TakeoMinad(RⅨEN),Dr.Kazul〕itoTsukagoshi(RⅡくEN),andDr.MasafU加Tamura(RIKEN)forcriticalcommentsanddiscussions.Thisworkwas

PartiaⅡysupportedbyaGrant-in-Aidforscientj員CResearch(NOS.16GS0219,17069003,18028029,and19360009)from山eMiniS四of副Ucation,culture,sports,scie"ce,aηdTechn010gyofJaP釦.1twasa】soparda11ysupp01'tedbyInduslrialTechn010oyResearchGra111Programin2006from小eNewEnergyandlnduSι"a】Techn010gyDevelopingor菖a-nizati0Π(NEDO)ofJapan.

Supportin雪lnfornlationAvailable:X・raydatainclFform且t飢denergybal}dst皿Cturesforla,1b,cis-2,a11dtra"S-2(PDnThismate亘祉isaV祉lablefreeofcha工oevia壮lelntemetat

hnp:ノノPubs.acs.org

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