Reduced Knoevenagel Reaction of Acetetracenylene-1,2-dione with Acceptor Units for Luminescent Tetracene Derivatives

Article abstract of DOI:10.1021/acs.joc.8b03083

Acetetracenylene-1,2-dione reacted with 3-ethylrhodanine in the presence of piperidine and Hantzsch ester via a Knoevenagel condensation-reduction sequence to give a tetracene-rhodanine adduct. This reduced Knoevenagel product exhibited magenta luminescence with a fluorescence quantum yield of = 0.34 and fluorescence lifetime of = 13.2 ns in toluene. Electrochemical studies and charge carrier transport measurements revealed ambipolar properties with hole and electron mobilities of 5.1 × 10^-7 and 1.6 × 10^-4 cm²/(V s), respectively.

Full text of DOI:10.1021/acs.joc.8b03083

Subscriber access provided by Iowa State University | Library
Note
Reduced Knoevenagel Reaction of Acetetracenylene-1,2-dione
with Acceptor Units for Luminescent Tetracene Derivatives
Yutaka Matsuo, Chu-Guo Yu, Takafumi Nakagawa, Hiroshi
Okada, Hiroshi Ueno, Tian-Ge Sun, and Yu-Wu Zhong
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b03083 • Publication Date (Web): 18 Jan 2019
Downloaded from http://pubs.acs.org on January 18, 2019
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a service to the research community to expedite the dissemination
of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in
full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully
peer reviewed, but should not be considered the official version of record. They are citable by the
Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,
the “Just Accepted” Web site may not include all articles that will be published in the journal. After
a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web
site and published as an ASAP article. Note that technical editing may introduce minor changes
to the manuscript text and/or graphics which could affect content, and all legal disclaimers and
ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or
consequences arising from the use of information contained in these “Just Accepted” manuscripts.
is published by the American Chemical Society. 1155 Sixteenth Street N.W.,
Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 7
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
Reduced Knoevenagel Reaction of Acetetracenylene-1,2-dione with
Acceptor Units for Luminescent Tetracene Derivatives
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
,
1,2
1
2
2
3
YutakaꢀMatsuo* ,ꢀChu-GuoꢀYu ,ꢀTakafumiꢀNakagawa ,ꢀHiroshiꢀOkada ,ꢀHiroshiꢀUeno ,ꢀTian-Geꢀ
4
4
Sun ,ꢀYu-WuꢀZhong ꢀ
1ꢀ
HefeiꢀNationalꢀLaboratoryꢀforꢀPhysicalꢀSciencesꢀatꢀMicroscale,ꢀandꢀDepartmentꢀofꢀChemistry,ꢀSchoolꢀofꢀChemistryꢀ
andꢀMaterialsꢀScience,ꢀUniversityꢀofꢀScienceꢀandꢀTechnologyꢀofꢀChina,ꢀ96ꢀJinzhaiꢀRoad,ꢀHefei,ꢀAnhuiꢀ230026,ꢀChinaꢀ
2ꢀ
DepartmentꢀofꢀMechanicalꢀEngineering,ꢀSchoolꢀofꢀEngineering,ꢀTheꢀUniversityꢀofꢀTokyo,ꢀ7-3-1ꢀHongo,ꢀBunkyo-ku,ꢀ
Tokyoꢀ113-8656,ꢀJapanꢀ
3ꢀ
4ꢀ
ꢀ
SchoolꢀofꢀChemistry,ꢀNortheastꢀNormalꢀUniversity,ꢀ5268ꢀRenminꢀStreet,ꢀChangchun,ꢀJilinꢀ130024,ꢀChinaꢀ
KeyꢀLaboratoryꢀofꢀPhotochemistry,ꢀInstituteꢀofꢀChemistry,ꢀChineseꢀAcademyꢀofꢀSciences,ꢀBeijingꢀ100190,ꢀChinaꢀ
SupportingꢀInformationꢀPlaceholderꢀ
S
Reduced Knoevenagel Reaction
N
S
3
-ethylrhodanine
O
O
O
piperidine
O
Hantzsch ester
ambipolar charge transport
µh = 5.1 x 10–7 cm /Vs
2
tetracene–rhodanine µe = 1.6 x 10–4 cm /Vs
2
non-fluorescent
fluorescent
ꢀ
ABSTRACT:ꢀAcetetracenylene-1,2-dioneꢀreactedꢀwithꢀ3-ethylrhodanineꢀinꢀtheꢀpresenceꢀofꢀpiperidineꢀandꢀHantzschꢀesterꢀviaꢀ
aꢀKnoevenagelꢀcondensation–reductionꢀsequenceꢀtoꢀgiveꢀaꢀtetracene–rhodanineꢀadduct.ꢀThisꢀreducedꢀKnoevenagelꢀproductꢀ
exhibitedꢀmagentaꢀluminescenceꢀwithꢀfluorescenceꢀquantumꢀyieldꢀofꢀφꢀ=ꢀ0.34ꢀandꢀfluorescenceꢀlifetimeꢀofꢀτꢀ=ꢀ13.2ꢀnsꢀinꢀtolu-
ene.ꢀElectrochemicalꢀstudiesꢀandꢀchargeꢀcarrierꢀtransportꢀmeasurementsꢀrevealedꢀambipolarꢀpropertiesꢀwithꢀholeꢀandꢀelec-
–
7
–4
2
tronꢀmobilitiesꢀofꢀ5.1ꢀ´ꢀ10 ꢀandꢀ1.6ꢀ´ꢀ10 ꢀcm /(Vꢀs),ꢀrespectively.ꢀꢀ
1
0
Tetraceneꢀ isꢀ aꢀ polycyclicꢀ aromaticꢀ hydrocarbonꢀ com-
posedꢀofꢀfourꢀlinearlyꢀfusedꢀbenzeneꢀrings,ꢀfallingꢀbetweenꢀ
theꢀ sizeꢀ ofꢀ anthraceneꢀ (threeꢀ rings)ꢀ andꢀ pentaceneꢀ (fiveꢀ
rings).ꢀFunctionalizationꢀofꢀtetraceneꢀisꢀanꢀintriguingꢀsub-
jectꢀ becauseꢀ itꢀ hasꢀ greaterꢀ stabilityꢀ duringꢀ handlingꢀ thanꢀ
pentaceneꢀ andꢀ isꢀ lessꢀ wellꢀ exploredꢀ thanꢀ anthraceneꢀ inꢀ
termsꢀofꢀderivatization.ꢀModificationꢀofꢀtetraceneꢀhasꢀbeenꢀ
bandgapꢀsmall-moleculeꢀdonors ꢀandꢀnon-fullereneꢀaccep-
1
1
tors. ꢀRhodanineꢀalsoꢀoffersꢀeasyꢀfunctionalizationꢀbecauseꢀ
ofꢀitsꢀactiveꢀmethyleneꢀatꢀtheꢀ5-position,ꢀwhichꢀactsꢀasꢀaꢀnu-
cleophileꢀandꢀattacksꢀC=Oꢀdoubleꢀbondsꢀforꢀconstructingꢀπ-
conjugatedꢀstructures.ꢀꢀ
Toꢀexploreꢀtheꢀmodificationꢀofꢀtetracene,ꢀhereꢀweꢀaimedꢀ
toꢀsynthesizeꢀaꢀlinkedꢀmoleculeꢀofꢀtetraceneꢀandꢀrhodanine.ꢀ
Duringꢀthisꢀresearch,ꢀanꢀunexpectedꢀKnoevenagelꢀconden-
sation–reductionꢀ occurredꢀ betweenꢀ acetetracenylene-1,2-
1
investigatedꢀ forꢀ π-systemꢀ expansionꢀ toꢀ nano-graphenes ꢀ
2
andꢀfusedꢀπ-systems, ꢀconstructionꢀofꢀfusedꢀdonor–acceptorꢀ
3
4
systemsꢀ forꢀ lightꢀ harvesting, ꢀ andꢀ otherꢀ purposes .ꢀ Ex-
pectedꢀapplicationsꢀofꢀtetraceneꢀderivativesꢀincludeꢀchargeꢀ
12
dione ꢀandꢀrhodanineꢀtoꢀproduceꢀaꢀluminescentꢀtetracene-
rhodanineꢀadduct.ꢀWeꢀalsoꢀuseꢀotherꢀnucleophilesꢀtoꢀsyn-
thesizeꢀadditionalꢀluminescentꢀtetraceneꢀderivativesꢀtoꢀin-
vestigateꢀtheꢀscopeꢀofꢀtheꢀreactionꢀandꢀtheꢀfunctionalꢀprop-
ertiesꢀofꢀtheꢀderivatives.ꢀThisꢀstudyꢀprovidesꢀusefulꢀinfor-
mationꢀ onꢀ theꢀ modificationꢀ ofꢀ tetraceneꢀ forꢀ constructingꢀ
acene-basedꢀluminescentꢀfunctionalꢀmaterials.ꢀ
5
6
carrierꢀtransportꢀmaterials, ꢀorganicꢀsolarꢀcells, ꢀandꢀsingletꢀ
7
fission .ꢀTheꢀluminescenceꢀofꢀtetraceneꢀderivativesꢀhasꢀnotꢀ
3
a,7a,ꢀ 8
beenꢀ extensivelyꢀ studied,
quantumꢀyieldꢀofꢀtetraceneꢀitselfꢀisꢀnotꢀhighꢀ(φꢀ=ꢀ0.118ꢀinꢀ
dichloromethane;ꢀφꢀ=ꢀ0.17ꢀinꢀbenzene).ꢀ3a,7a
ꢀ becauseꢀ theꢀ fluorescenceꢀ
ꢀ
Rhodanineꢀhasꢀbeenꢀwidelyꢀusedꢀinꢀdyeꢀchemistryꢀtoꢀcon-
structꢀpush-pullꢀchromophores. ꢀItꢀhasꢀrecentlyꢀbeenꢀusedꢀ
asꢀ anꢀ electron-withdrawingꢀ endcapꢀ toꢀ constructꢀ low-
Startingꢀfromꢀaꢀtetraceneꢀdiketone,ꢀacetetracenylene-1,2-
dioneꢀ(1),ꢀweꢀfirstꢀattemptedꢀtheꢀKnoevenagelꢀcondensationꢀ
withꢀ 3-ethylrhodanineꢀ (2)ꢀ inꢀ theꢀ presenceꢀ ofꢀ piperidineꢀ
9
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 2 of 7
withꢀtheꢀaimꢀofꢀobtainingꢀaꢀconjugatedꢀdonorꢀ(tetracene)–
Schemeꢀ1.ꢀReducedꢀKnoevenagelꢀreactionꢀbyꢀusingꢀpiperidineꢀ
andꢀHantzschꢀesterꢀtoꢀobtainꢀtetraceneꢀderivativesꢀwithꢀelec-
tron-withdrawingꢀgroups.ꢀꢀ
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
acceptorꢀ(rhodanine)ꢀadductꢀ(Schemeꢀ1,ꢀtop).ꢀToꢀourꢀsur-
prise,ꢀweꢀobtainedꢀaꢀreducedꢀproductꢀ(3)ꢀinsteadꢀofꢀtheꢀex-
pectedꢀ Knoevenagelꢀ condensationꢀ product.ꢀ Reducedꢀ
Knoevenagelꢀ condensationꢀ productsꢀ haveꢀ beenꢀ reportedꢀ
1
13
Productꢀ3ꢀwasꢀcharacterizedꢀbyꢀ Hꢀandꢀ CꢀNMRꢀspectros-
copy,ꢀ2DꢀNMR,ꢀandꢀhigh-resolutionꢀESI-TOFꢀmassꢀspectrom-
1
3
previously, ꢀ andꢀ formꢀ viaꢀ reductionꢀ ofꢀ theꢀ Knoevenagelꢀ
condensationꢀproduct.ꢀHantzschꢀesterꢀisꢀoftenꢀusedꢀasꢀanꢀin-
expensiveꢀcommerciallyꢀavailableꢀreducingꢀreagentꢀforꢀthisꢀ
reductionꢀ reaction.ꢀ Thus,ꢀ weꢀ usedꢀ Hantzschꢀ esterꢀ toꢀ im-
proveꢀ theꢀ reproducibilityꢀ ofꢀ theꢀ synthesis.ꢀ Theꢀ productꢀ
couldꢀbeꢀpurifiedꢀbyꢀsilicaꢀgelꢀcolumnꢀchromatographyꢀtoꢀ
separateꢀitꢀfromꢀtheꢀreactionꢀmixtureꢀcontainingꢀunreactedꢀ
startingꢀmaterialꢀ1.ꢀCompoundꢀ3ꢀwasꢀobtainedꢀasꢀanꢀair-sta-
bleꢀ deep-redꢀ powderꢀ inꢀ 42%ꢀ isolatedꢀ yield.ꢀ Weꢀ considerꢀ
thatꢀtheꢀKnoevenagelꢀcondensationꢀoccursꢀfirst,ꢀfollowedꢀbyꢀ
reductionꢀofꢀtheꢀintermediateꢀtoꢀgiveꢀtheꢀproduct.ꢀTheꢀprod-
uctꢀ3ꢀwasꢀmuchꢀmoreꢀsolubleꢀthanꢀpristineꢀtetraceneꢀandꢀ
tetraceneꢀdiketoneꢀ1ꢀinꢀvariousꢀsolvents.ꢀThisꢀwasꢀdueꢀtoꢀtheꢀ
solubleꢀrhodanineꢀaddendꢀandꢀtheꢀlowꢀcrystallinityꢀofꢀtheꢀ
product,ꢀwhichꢀwasꢀmixtureꢀofꢀtwoꢀdiastereomersꢀwithꢀre-
spectꢀtoꢀtwoꢀracemicꢀstereocenters.ꢀThisꢀimprovedꢀsolubil-
ityꢀisꢀbeneficialꢀforꢀsolutionꢀprocessingꢀtoꢀmakeꢀthinꢀfilmsꢀ
forꢀuseꢀinꢀorganicꢀelectronics.ꢀByꢀusingꢀ4ꢀ(indane-1,3-dione)ꢀ
andꢀ5ꢀ(2-thioxo-dihydro-pyrimidine-4,6-dione)ꢀasꢀalterna-
tiveꢀnucleophilesꢀunderꢀtheꢀsameꢀreactionꢀconditions,ꢀweꢀ
synthesizedꢀreducedꢀKnoevenagelꢀcondensationꢀproductsꢀ6ꢀ
inꢀfairꢀyieldꢀandꢀ7ꢀinꢀgoodꢀyield,ꢀrespectively.ꢀWithꢀtheꢀad-
vantageꢀofꢀhavingꢀtwoꢀcarbonylꢀgroupsꢀonꢀtheseꢀaddends,ꢀ6ꢀ
andꢀ7ꢀwereꢀeasierꢀthanꢀ3ꢀtoꢀseparateꢀbyꢀsilicaꢀgelꢀcolumnꢀ
chromatography,ꢀowingꢀtoꢀtheirꢀfavorableꢀpolarity.ꢀ
1
etry.ꢀTheꢀ HꢀNMRꢀspectrumꢀdisplayedꢀaꢀsignalꢀpatternꢀofꢀaꢀ
diastereomericꢀ mixtureꢀ withꢀ aꢀ major/minorꢀ ratioꢀ ofꢀ 4:1ꢀ
(FigureꢀS2).ꢀTheꢀspectrumꢀcontainedꢀ10ꢀprotonꢀsignalsꢀas-
signedꢀ toꢀ theꢀ asymmetricꢀ tetraceneꢀ moietyꢀ andꢀ aꢀ pairꢀ ofꢀ
doubletꢀsignalsꢀassignedꢀtoꢀtheꢀmethineꢀprotonsꢀofꢀtheꢀre-
ducedꢀpartꢀatꢀ5.40ꢀandꢀ5.26ꢀppmꢀwithꢀaꢀcouplingꢀconstantꢀJꢀ
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
13
=
ꢀ3.2ꢀHzꢀinꢀchloroform-d.ꢀTheꢀ CꢀNMRꢀsignalsꢀforꢀtheꢀre-
ducedꢀpartꢀappearedꢀatꢀ51.02ꢀandꢀ53.21ꢀppm,ꢀcorrespond-
3
ingꢀtoꢀsp ꢀmethineꢀcarbonsꢀandꢀconfirmingꢀtheꢀformationꢀofꢀ
theꢀ reducedꢀ Knoevenagelꢀ product.ꢀ Thermalꢀ stabilityꢀ wasꢀ
confirmedꢀ byꢀ thermogravimetricꢀ analysis,ꢀ whichꢀ showedꢀ
thatꢀ3ꢀwasꢀstableꢀupꢀtoꢀaroundꢀ250ꢀ°Cꢀ(FigureꢀS14).ꢀ
Compoundsꢀ6ꢀandꢀ7ꢀwereꢀalsoꢀcharacterizedꢀbyꢀspectro-
scopicꢀmethods.ꢀBothꢀ6ꢀandꢀ7ꢀwereꢀeasilyꢀidentifiedꢀbyꢀsim-
1
pleꢀ HꢀNMRꢀspectroscopy,ꢀbecauseꢀtheseꢀcompoundsꢀwereꢀaꢀ
racemicꢀmixtureꢀofꢀtwoꢀenantiomers,ꢀnotꢀaꢀdiastereomericꢀ
mixture.ꢀThisꢀmeritꢀcomesꢀfromꢀtheꢀuseꢀofꢀsymmetricꢀactiveꢀ
1
methyleneꢀcompoundsꢀ4ꢀandꢀ5.ꢀNoteꢀthat,ꢀinꢀtheꢀ HꢀNMRꢀ
spectrumꢀofꢀ7,ꢀtheꢀtwoꢀethylꢀgroupsꢀappearedꢀatꢀdifferentꢀ
chemicalꢀshiftsꢀdueꢀtoꢀrestrictedꢀrotationꢀaroundꢀtheꢀsingleꢀ
bondꢀaxis,ꢀandꢀtwoꢀprotonꢀsignalsꢀofꢀtheꢀtwoꢀhydrogenꢀat-
omsꢀonꢀtheꢀα-carbonꢀofꢀtheꢀethylꢀgroupsꢀwereꢀfoundꢀtoꢀbeꢀ
non-equivalentꢀbecauseꢀofꢀtheirꢀdiastereotopicꢀrelationshipꢀ
withꢀtheꢀacetetracenylene’sꢀmethineꢀcarbon.ꢀ
Afterꢀ considerableꢀ experimentation,ꢀ weꢀ foundꢀ thatꢀ
Knoevenagelꢀcondensationꢀproductꢀ6′ꢀcouldꢀbeꢀisolatedꢀasꢀ
anꢀ intermediateꢀ inꢀ theꢀ formationꢀ ofꢀ 6ꢀ inꢀ theꢀ absenceꢀ ofꢀ
Hantzschꢀ ester.ꢀ Theꢀ conjugatedꢀ productꢀ 6′ꢀ graduallyꢀ de-
gradedꢀinꢀsolutionꢀinꢀair,ꢀwhereasꢀcompoundꢀ6ꢀwasꢀmoreꢀ
stable.ꢀ Weꢀ identifiedꢀ 6′ꢀbyꢀ NMRꢀ andꢀ high-resolutionꢀ ESI-
ꢀ
S
N
S
piperidine (20 mol %)
O
O
DMSO
9
0 °C, 4 h
1
TOFꢀMSꢀspectroscopyꢀ(SupportingꢀInformation).ꢀInꢀ HꢀNMRꢀ
piperidine
Hantzsch ester
EtOOC COOEt
S
andꢀESIꢀmassꢀspectrometry,ꢀweꢀobservedꢀthatꢀ6′ꢀwasꢀob-
tainedꢀasꢀaꢀcomplexꢀwithꢀindane-1,3-dioneꢀ4ꢀthroughꢀstrongꢀ
hydrogenꢀbondingꢀbetweenꢀtheꢀtwoꢀacidicꢀ(δ+)ꢀprotonsꢀandꢀ
theꢀtwoꢀcarbonylꢀgroupsꢀ(FigureꢀS12).ꢀWeꢀsurmiseꢀthatꢀthisꢀ
intermolecularꢀinteractionꢀisꢀvitalꢀforꢀtheꢀstabilityꢀofꢀ6′.ꢀByꢀ
reactingꢀtheꢀisolatedꢀcomplexꢀofꢀ6′ꢀandꢀ4ꢀwithꢀHantzschꢀes-
terꢀ(1.0ꢀequiv)ꢀandꢀpiperidineꢀ(10ꢀmolꢀ%)ꢀinꢀDMSOꢀforꢀ1ꢀhꢀ
atꢀ60ꢀ°C,ꢀweꢀconfirmedꢀthatꢀ6′ꢀwasꢀconvertedꢀtoꢀ6ꢀinꢀ63%ꢀ
yieldꢀ(SchemeꢀS1).ꢀ
N
S
O
O
N
H
O
N
H
O
S
N
(20 mol %)
(1.5 equiv)
+
S
O
DMSO, 60 °C, 8 h
1
2 (1.2 equiv)
3, 42%
S
S
S
S
H
N
N
H
O
H
O
O
H
O
TheꢀUV-visꢀspectrumꢀofꢀ3ꢀinꢀdichloromethaneꢀexhibitedꢀaꢀ
broadꢀabsorptionꢀspectrumꢀextendingꢀupꢀtoꢀ600ꢀnm,ꢀwithꢀ
absorptionꢀmaximaꢀatꢀ390,ꢀ411,ꢀ510,ꢀandꢀ540ꢀnmꢀ(Figureꢀ
1a).ꢀThisꢀspectralꢀpatternꢀofꢀ3ꢀresembledꢀthatꢀofꢀtheꢀstartingꢀ
materialꢀ 1,ꢀ indicatingꢀ theꢀ tetraceneꢀ π-conjugatedꢀ systemꢀ
wasꢀ retainedꢀ duringꢀ theꢀ reaction.ꢀ Compoundꢀ 3ꢀ exhibitedꢀ
magentaꢀ luminescence.ꢀ Itsꢀ fluorescenceꢀ spectrumꢀ wasꢀ
broad,ꢀ rangingꢀ fromꢀ 520ꢀ toꢀ 800ꢀ nmꢀ withꢀ aꢀ maximumꢀ atꢀ
aboutꢀ580ꢀnmꢀandꢀshouldersꢀatꢀaboutꢀ625ꢀandꢀ690ꢀnmꢀinꢀ
dichloromethaneꢀ (Figureꢀ 1b).ꢀ Theꢀ absoluteꢀ fluorescenceꢀ
quantumꢀyieldꢀandꢀfluorescenceꢀlifetimeꢀwereꢀφꢀ=ꢀ0.23ꢀandꢀ
τꢀ=ꢀ10.4ꢀns,ꢀrespectively,ꢀinꢀdichloromethane,ꢀandꢀφꢀ=ꢀ0.34ꢀ
andꢀ τꢀ =ꢀ 13.2ꢀ ns,ꢀ respectively,ꢀ inꢀ tolueneꢀ (Tableꢀ S1).ꢀ Thisꢀ
diastereomers of 3
S
N
S
N
N
O
O
or
O
O
N
O
O
O
O
4
5
O
O
(1.2 equiv)
or
piperidine (20 mol %)
Hantzsch ester (1.5 equiv)
DMSO, 60 °C, 8 h
6, 56%
7, 71%
Hantzsch ester
(1.0 equiv)
O
y, 63%
H
O
O
O
H
O
O
O
4
(1.2 equiv)
O
piperidine (20 mol %)
DMSO, 60 °C, 8 h
6
', 47%
14
6'+4
compoundꢀ displayedꢀ solvato-fluorochromism ꢀ inꢀ whichꢀ
ꢀ
theꢀcolorꢀchangedꢀaccordingꢀtoꢀtheꢀpolarityꢀofꢀtheꢀsolventꢀ
(Figureꢀ 1c,d).ꢀ Thisꢀ phenomenonꢀ indicatesꢀ thatꢀ
ACS Paragon Plus Environment

Page 3 of 7
The Journal of Organic Chemistry
–
5
intramolecularꢀchargeꢀtransferꢀ(ICT)ꢀcontributedꢀtoꢀtheꢀflu-
orescence; ꢀspecifically,ꢀtheꢀcharge-transferꢀstateꢀwasꢀsta-
roomꢀtemperatureꢀwithꢀconcentrationꢀofꢀ1ꢀxꢀ10 ꢀM.ꢀ(a)ꢀUV-visꢀ
absorptionꢀspectrum.ꢀAbsorptionꢀmaximaꢀinꢀtheꢀspectrumꢀforꢀ
3ꢀareꢀ380,ꢀ411,ꢀ510,ꢀ540ꢀnm.ꢀAꢀgrayꢀdashedꢀlineꢀdenotesꢀanꢀab-
sorptionꢀspectrumꢀofꢀ1ꢀinꢀtheꢀsameꢀcondition.ꢀ(b)ꢀNormalizedꢀ
1
2
3
4
5
6
7
8
9
15
bilizedꢀ inꢀ moreꢀ polarꢀ solvents,ꢀ thusꢀ loweringꢀ theꢀ energyꢀ
levelꢀ ofꢀ theꢀ excitedꢀ singletꢀ stateꢀ andꢀ causingꢀ red-shiftedꢀ
emissions.ꢀ Weꢀ considerꢀ thatꢀ thisꢀ ICTꢀ occursꢀ fromꢀ theꢀ te-
traceneꢀdonorꢀtoꢀtheꢀaddendꢀacceptor.ꢀNoteꢀthatꢀtheꢀstartingꢀ
materialꢀ1ꢀwasꢀalmostꢀnon-luminescent.ꢀWeꢀsurmiseꢀthatꢀin-
stallationꢀofꢀtheꢀrhodanineꢀgroupꢀsignificantlyꢀaffectedꢀtheꢀ
excitedꢀstateꢀbyꢀchangingꢀtheꢀcharge-transferꢀproperties.ꢀꢀ
–
5
fluorescenceꢀspectraꢀ(10 ꢀM)ꢀatꢀroomꢀtemperatureꢀexcitedꢀatꢀ
10ꢀnm.ꢀ(c)ꢀSolvato-fluorochromismꢀofꢀ3.ꢀFromꢀleftꢀtoꢀright,ꢀn-
hexane,ꢀ toluene,ꢀ THF,ꢀ dichloromethane,ꢀ andꢀ acetonitrile.ꢀ
5
(
d)Normalizedꢀfluorescenceꢀspectraꢀofꢀ3ꢀinꢀvariousꢀsolvents.ꢀꢀ
Compoundsꢀ6,ꢀ6′,ꢀandꢀ7ꢀshowedꢀsimilarꢀUV-visꢀabsorp-
tionꢀandꢀfluorescenceꢀspectraꢀ(Figureꢀ1a),ꢀbutꢀ6′ꢀhadꢀslightlyꢀ
red-shiftedꢀabsorptionꢀandꢀemission.ꢀThisꢀredꢀshiftꢀwasꢀ20–
(
a)ꢀ
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
30ꢀnmꢀandꢀwasꢀcausedꢀbyꢀtheꢀcentralꢀdoubleꢀbondꢀinꢀ6′ꢀex-
tendingꢀ theꢀ π-conjugation.ꢀ Theꢀ fluorescenceꢀ quantumꢀ
yieldsꢀandꢀfluorescenceꢀlifetimesꢀofꢀ6,ꢀ6′,ꢀandꢀ7ꢀwereꢀsimilarꢀ
toꢀthoseꢀofꢀ3:ꢀφꢀ=ꢀ0.25,ꢀ0.19,ꢀandꢀ0.24ꢀandꢀτꢀ=ꢀ11.0,ꢀ8.7,ꢀandꢀ
10.5ꢀnsꢀforꢀ6,ꢀ6′,ꢀandꢀ7,ꢀrespectively,ꢀunderꢀtheꢀsameꢀcondi-
tionsꢀ(TableꢀS1).ꢀ
Next,ꢀweꢀinvestigatedꢀtheꢀelectrochemicalꢀpropertiesꢀofꢀ3,ꢀ
6,ꢀ6′,ꢀandꢀ7.ꢀCyclicꢀvoltammetryꢀ(CV)ꢀofꢀtheꢀcompoundsꢀinꢀ
dichloromethaneꢀclearlyꢀshowedꢀreversibleꢀoxidationꢀpro-
cessesꢀ forꢀ theseꢀ compoundꢀ (Figureꢀ S22).ꢀ However,ꢀ theseꢀ
compoundsꢀexhibitedꢀirreversibleꢀreductionꢀwaves.ꢀThisꢀisꢀ
likelyꢀbecauseꢀofꢀtautomerizationꢀfromꢀtheꢀdiketoneꢀformꢀtoꢀ
aꢀdiolꢀformꢀwithꢀaꢀdieneꢀstructure,ꢀfromꢀwhichꢀaꢀhydrogenꢀ
atomꢀ canꢀ beꢀ removedꢀ inꢀ theꢀ reductionꢀ processꢀ toꢀ formꢀ
ꢀ
(b)ꢀ
–
alkoxideꢀ(–O )ꢀ(FigureꢀS23).ꢀHowever,ꢀtheseꢀreductionꢀpo-
tentialsꢀappearedꢀasꢀpeaksꢀinꢀdifferentialꢀpulseꢀvoltammetryꢀ
(DPV;ꢀFigureꢀ2).ꢀFromꢀtheseꢀDPVꢀdata,ꢀweꢀcouldꢀestimateꢀtheꢀ
frontierꢀorbitalꢀenergyꢀlevelsꢀfromꢀtheꢀequationsꢀHOMOꢀ=ꢀ–
ox1
(
4.8ꢀ+ꢀE1/2 )ꢀandꢀLUMOꢀ=ꢀ–(4.8ꢀ+ꢀE1/2red1)ꢀeVꢀandꢀtheꢀelec-
16
trochemicalꢀbandgap. ꢀTheꢀHOMOꢀandꢀLUMOꢀenergyꢀlevelsꢀ
ofꢀtheseꢀcompoundsꢀwereꢀ–5.51ꢀtoꢀ–5.56ꢀeVꢀandꢀ–3.26ꢀtoꢀ–
3
.33ꢀeV,ꢀrespectively,ꢀsuggestingꢀtheseꢀmaterialsꢀareꢀambi-
6
polar. ꢀ Theꢀ electrochemicalꢀ bandgapsꢀ ofꢀ 2.18ꢀ toꢀ 2.26ꢀ eVꢀ
wereꢀalmostꢀidenticalꢀtoꢀthoseꢀdeterminedꢀfromꢀtheꢀabsorp-
tionꢀonset,ꢀE ꢀ=ꢀ1240/λonsetꢀ=ꢀ2.10ꢀeV.ꢀTheseꢀbandgapsꢀareꢀ
g
smallerꢀthanꢀtheꢀbandgapꢀofꢀpristineꢀtetraceneꢀ(2.50ꢀeV).ꢀ
ꢀ
(c)ꢀ
ꢀ
(d)ꢀ
ꢀ
Figureꢀ2.ꢀElectrochemicalꢀdataꢀ(DPV)ꢀinꢀdichloromethaneꢀcon-
tainingꢀ0.1ꢀMꢀTBAPF .ꢀ
6
ꢀ
Figureꢀ1.ꢀUV-visꢀandꢀfluorescentꢀspectraꢀofꢀ3,ꢀ6,ꢀ6′,ꢀandꢀ7ꢀ(blue,ꢀ
red,ꢀ black,ꢀ greenꢀ lines,ꢀ respectively)ꢀ inꢀ dichloromethaneꢀ inꢀ
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Toꢀvisualizeꢀtheꢀdistributionꢀofꢀfrontierꢀmolecularꢀorbit-
Page 4 of 7
Figureꢀ3.ꢀOptimizedꢀstructuresꢀforꢀmajorꢀandꢀminorꢀisomersꢀofꢀ
3ꢀ(AꢀandꢀB)ꢀwithꢀHOMOꢀandꢀLUMOꢀdistributionꢀ(B3LYPꢀwithꢀaꢀ
6-31G(d)ꢀbasisꢀset).ꢀ(a)ꢀTopꢀviewꢀofꢀA.ꢀ(b)ꢀTopꢀviewꢀofꢀB.ꢀ(c)ꢀ
SideꢀviewꢀofꢀA.ꢀ(d)ꢀSideꢀviewꢀofꢀB.ꢀ(e)ꢀCalculatedꢀHOMOꢀdistri-
butionꢀofꢀcomputationallyꢀmoreꢀstableꢀisomerꢀA.ꢀ(f)ꢀCalculatedꢀ
LUMOꢀdistributionꢀofꢀA.ꢀ(g)ꢀCalculatedꢀLUMO+1ꢀdistributionꢀofꢀ
A.ꢀ(h)ꢀCalculatedꢀLUMO+2ꢀdistributionꢀofꢀA.ꢀ
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
als,ꢀweꢀperformedꢀcomputationalꢀcalculationsꢀinꢀtheꢀGauss-
ian09ꢀprogramꢀusingꢀdensityꢀfunctionalꢀtheoryꢀ(DFT)ꢀatꢀtheꢀ
B3LYP/6-31G(d)ꢀ level.ꢀ First,ꢀ weꢀ optimizedꢀ theꢀ twoꢀ dia-
stereomericꢀstructuresꢀofꢀ3ꢀ(Figureꢀ3a-d).ꢀIsomerꢀAꢀ(acete-
tracenylene-S,ꢀrhodanine-S)ꢀwasꢀfoundꢀtoꢀbeꢀslightlyꢀmoreꢀ
stableꢀ thanꢀ isomerꢀ Bꢀ (acetetracenylene-R,ꢀ rhodanine-S),ꢀ
withꢀaꢀsmallꢀdifferenceꢀinꢀGibbsꢀfreeꢀenergyꢀofꢀ3.4ꢀkJ/mol.ꢀ
Weꢀdoꢀnotꢀconsiderꢀhereꢀwhichꢀdiastereomerꢀisꢀtheꢀmajorꢀ
isomerꢀinꢀtheꢀreaction.ꢀTheꢀtetraceneꢀplaneꢀandꢀtheꢀsulfurꢀ
atomꢀinꢀtheꢀfive-memberedꢀringꢀofꢀrhodanineꢀareꢀinꢀaꢀstag-
geredꢀconformationꢀinꢀtheꢀoptimizedꢀstructuresꢀofꢀbothꢀAꢀ
andꢀB.ꢀTheꢀcalculatedꢀHOMOꢀandꢀLUMOꢀdistributionsꢀofꢀtheꢀ
isomerꢀ Aꢀ areꢀ shownꢀ inꢀ Figureꢀ 3e,f.ꢀ Bothꢀ theꢀ HOMOꢀ andꢀ
LUMOꢀareꢀlocatedꢀmainlyꢀonꢀtheꢀtetraceneꢀmoietyꢀinꢀconju-
gationꢀwithꢀtheꢀcarbonylꢀgroup.ꢀLUMO+1ꢀappearsꢀpredomi-
nantlyꢀonꢀtheꢀrhodanineꢀunitꢀwhileꢀLUMO+2ꢀappearsꢀpartlyꢀ
onꢀitꢀ(Figureꢀ3g,h).ꢀThus,ꢀweꢀconsiderꢀICTꢀcouldꢀoccurꢀfromꢀ
theꢀHOMOꢀtoꢀLUMO+1,ꢀwhileꢀtheꢀHOMO–LUMOꢀtransitionꢀisꢀ
alsoꢀfavorableꢀbecauseꢀofꢀitsꢀlowꢀtransitionꢀenergyꢀandꢀtheꢀ
similarityꢀofꢀtheꢀHOMOꢀandꢀLUMOꢀdistributions.ꢀTheꢀcalcu-
latedꢀHOMO/LUMOꢀenergyꢀlevelsꢀofꢀAꢀandꢀBꢀwereꢀ–5.32/–
Computationalꢀstudiesꢀwereꢀalsoꢀperformedꢀforꢀ6,ꢀ6′,ꢀandꢀ
7ꢀtoꢀelucidateꢀtheirꢀluminescentꢀpropertiesꢀ(FiguresꢀS24–
27).ꢀAmongꢀtheꢀthreeꢀcompounds,ꢀonlyꢀcompoundꢀ6′ꢀhadꢀ
theꢀLUMOꢀdistributedꢀonꢀbothꢀtheꢀaddendꢀandꢀtheꢀtetraceneꢀ
unit.ꢀTheꢀLUMOꢀdistributionꢀofꢀ6ꢀandꢀ7ꢀwasꢀsimilarꢀtoꢀthatꢀ
ofꢀ3,ꢀwhereꢀtheꢀLUMOꢀwasꢀlocatedꢀonꢀtheꢀtetraceneꢀdonorꢀ
andꢀLUMO+1ꢀwasꢀlocatedꢀonꢀtheꢀaddendꢀacceptor.ꢀꢀ
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
17
Space-chargeꢀlimitedꢀcurrentꢀ(SCLC) ꢀmobilityꢀmeasure-
mentsꢀwereꢀperformedꢀtoꢀevaluateꢀtheꢀchargeꢀcarrierꢀmo-
bilityꢀofꢀ3.ꢀWeꢀfabricatedꢀhole-onlyꢀandꢀelectron-onlyꢀde-
vicesꢀ withꢀ configurationsꢀ ofꢀ ITO/PEDOT:PSS/3/MoO /Alꢀ
3
1
8
andꢀAl/3/Al, ꢀrespectivelyꢀ(FiguresꢀS28ꢀandꢀS29).ꢀTheꢀhighꢀ
solubilityꢀdueꢀtoꢀthisꢀcompoundꢀbeingꢀpresentꢀasꢀaꢀdiastere-
omericꢀ mixtureꢀ wasꢀ beneficialꢀ forꢀ fabricatingꢀ thinꢀ films.ꢀ
Compoundꢀ3ꢀwasꢀspin-coatedꢀfromꢀaꢀ20ꢀmg/mLꢀsolutionꢀinꢀ
dichloromethane.ꢀAfterꢀannealingꢀatꢀ60ꢀ°Cꢀforꢀ10ꢀmin,ꢀgoodꢀ
filmsꢀwithoutꢀpin-holesꢀwereꢀobtainedꢀ(thickness:ꢀ60ꢀnm),ꢀ
2.79ꢀandꢀ–5.34/–2.81ꢀeV,ꢀrespectively.ꢀBothꢀAꢀandꢀBꢀhadꢀaꢀ
calculatedꢀbandgapꢀofꢀ2.53ꢀeV,ꢀwhichꢀisꢀlargerꢀthanꢀtheꢀval-
uesꢀobservedꢀfromꢀelectrochemicalꢀandꢀspectroscopicꢀstud-
ies.ꢀInꢀcomputationsꢀsuchꢀasꢀthis,ꢀcalculatedꢀbandgapsꢀtendꢀ
toꢀbeꢀhigherꢀthanꢀexperimentalꢀvalues.ꢀ
andꢀholeꢀandꢀelectronꢀmobilitiesꢀwereꢀdeterminedꢀtoꢀbeꢀμ ꢀ
h
–
7
–4
2
=
ꢀ5.1ꢀ´ꢀ10 ꢀandꢀμ ꢀ=ꢀ1.6ꢀ´ꢀ10 ꢀcm /(Vꢀs),ꢀrespectively.ꢀTheseꢀ
e
dataꢀsuggestꢀthatꢀthisꢀcompoundꢀcouldꢀbeꢀusefulꢀasꢀanꢀelec-
tronꢀ transportꢀ materialꢀ inꢀ variousꢀ thin-filmꢀ organicꢀ elec-
tronics.ꢀWeꢀattributeꢀthisꢀpropertyꢀmainlyꢀtoꢀtheꢀelectron-
withdrawingꢀ carbonylꢀ moietyꢀ attachedꢀ toꢀ theꢀ tetraceneꢀ
moietyꢀ andꢀ toꢀ theꢀ electron-withdrawingꢀ natureꢀ ofꢀ theꢀ
rhodanineꢀgroup.ꢀ
Inꢀ summary,ꢀ weꢀ demonstratedꢀ derivatizationꢀ ofꢀ te-
traceneꢀ diketoneꢀ (acetetracenylene-1,2-dione)ꢀ byꢀ aꢀ
Knoevenagelꢀ condensation–reductionꢀ sequenceꢀ usingꢀ theꢀ
nucleophilesꢀ 3-ethylrhodanine,ꢀ indane-1,3-dione,ꢀ andꢀ 2-
thioxo-dihydro-pyrimidine-4,6-dione.ꢀ Productꢀ 3ꢀ exhibitedꢀ
magentaꢀluminescenceꢀwithꢀaꢀbroadꢀfluorescenceꢀspectrum,ꢀ
aꢀfluorescenceꢀquantumꢀyieldꢀofꢀφꢀ=ꢀ0.34,ꢀandꢀaꢀfluorescenceꢀ
lifetimeꢀofꢀτꢀ=ꢀ13.2ꢀnsꢀ(inꢀtoluene),ꢀandꢀ6ꢀandꢀ7ꢀgaveꢀsimilarꢀ
luminesceꢀresults.ꢀSolvato-fluorochromismꢀwasꢀobservedꢀinꢀ
whichꢀtheꢀemissionꢀcolorꢀchangedꢀaccordingꢀtoꢀsolventꢀpo-
larity,ꢀowingꢀtoꢀICTꢀfromꢀtheꢀtetraceneꢀdonorꢀtoꢀtheꢀaddendꢀ
acceptor.ꢀTheꢀacceptableꢀsolubilityꢀofꢀtheseꢀcompoundsꢀwasꢀ
beneficialꢀforꢀfabricatingꢀthinꢀfilmsꢀofꢀgoodꢀquality.ꢀElectro-
chemicalꢀ andꢀ SCLCꢀ measurementsꢀ revealedꢀ ambipolarꢀ
properties,ꢀwithꢀholeꢀandꢀelectronꢀmobilitiesꢀofꢀμ
h
ꢀ=ꢀ5.1ꢀ´ꢀ
–
7
–4
2
1
0 ꢀandꢀμ
e
ꢀ=ꢀ1.6ꢀ´ꢀ10 ꢀcm /(Vꢀs),ꢀrespectively,ꢀforꢀ3.ꢀTheꢀ
betterꢀ electronꢀ mobilityꢀ thanꢀ holeꢀ mobilityꢀ suggestsꢀ thatꢀ
thisꢀtetraceneꢀcompoundꢀcouldꢀbeꢀusedꢀasꢀaꢀfluorescentꢀn-
typeꢀmaterialꢀinꢀorganicꢀelectronicsꢀdevices.ꢀThisꢀworkꢀwillꢀ
contributeꢀtoꢀtheꢀdesignꢀofꢀacene-basedꢀfunctionalꢀmaterialsꢀ
toꢀobtainꢀnewꢀorganicꢀsemiconductorsꢀforꢀphotoelectronicꢀ
applications.ꢀ
Experimental Section
GeneralꢀInformation.ꢀUnlessꢀotherwiseꢀnoted,ꢀallꢀmate-
rialsꢀincludingꢀdryꢀsolventsꢀwereꢀobtainedꢀfromꢀcommercialꢀ
suppliersꢀandꢀusedꢀwithoutꢀfurtherꢀpurification.ꢀUnlessꢀoth-
erwiseꢀ noted,ꢀ allꢀ reactionsꢀ wereꢀ performedꢀ withꢀ dryꢀ
ꢀ
ACS Paragon Plus Environment

Page 5 of 7
The Journal of Organic Chemistry
solventsꢀunderꢀanꢀatmosphereꢀofꢀargonꢀinꢀflame-driedꢀglass-
wareꢀwithꢀstandardꢀvacuum-lineꢀtechniques.ꢀ
8.04ꢀ(d,ꢀJꢀ=ꢀ8.7ꢀHz,ꢀ1H),ꢀ7.75–7.67ꢀ(m,ꢀ1H),ꢀ7.58ꢀ(dd,ꢀJꢀ=ꢀ15.7,ꢀ
9.2ꢀHz,ꢀ2H),ꢀ7.50–7.44ꢀ(m,ꢀ1H),ꢀ5.40ꢀ(d,ꢀJꢀ=ꢀ3.2ꢀHz,ꢀ1H),ꢀ5.26ꢀ
(d,ꢀJꢀ=ꢀ3.2ꢀHz,ꢀ1H),ꢀ4.23ꢀ(tt,ꢀJꢀ=ꢀ7.2,ꢀ3.6ꢀHz,ꢀ2H),ꢀ1.40ꢀ(t,ꢀJꢀ=ꢀ7.1ꢀ
1
2
3
4
5
6
7
8
9
AllꢀNMRꢀspectraꢀwereꢀtakenꢀatꢀ400ꢀMHzꢀ(BrukerꢀAVANCEꢀ
IIIꢀ 400ꢀ spectrometer).ꢀ Unlessꢀ otherwiseꢀ specified,ꢀ allꢀ theꢀ
NMRꢀ spectraꢀ wereꢀ recordedꢀ inꢀ partsꢀ perꢀ millionꢀ (ppm,ꢀ
ꢀ
13
1
Hz,ꢀ 3H). C{ H}ꢀ NMRꢀ (101ꢀ MHz,ꢀ CDCl
175.3,ꢀ141.8,ꢀ133.5,ꢀ133.4,ꢀ133.3,ꢀ130.6,ꢀ123.0,ꢀ129.4,ꢀ129.1,ꢀ
28.9,ꢀ127.7,ꢀ126.9,ꢀ126.6,ꢀ126.4,ꢀ125.9,ꢀ125.9,ꢀ125.5,ꢀ124.7,ꢀ
3
)ꢀ δꢀ 199.9,ꢀ 199.6,ꢀ
1
scale)ꢀ withꢀ theꢀ protonꢀ ofꢀ tetramethylsilaneꢀ (TMS)ꢀ (0.00ꢀ
+
ꢀ
1
122.8,ꢀ53.2,ꢀ51.0,ꢀ40.3,ꢀ11.8.ꢀHRMSꢀ(ESI-TOF)ꢀm/z:ꢀ[M+H ]
calcdꢀforꢀC25 NS ꢀ428.0774,ꢀfoundꢀ428.0772.ꢀ
ppm)ꢀforꢀ HꢀNMRꢀandꢀcarbonꢀofꢀCDCl
3
ꢀ(77.16ꢀppm)ꢀorꢀcar-
13
H
18
O
2
2
bonꢀofꢀDMSO-d
6
ꢀ(39.52ꢀppm)ꢀforꢀ CꢀNMRꢀasꢀinternalꢀrefer-
ence,ꢀrespectively.ꢀTheꢀdataꢀwereꢀpresentedꢀasꢀfollowingꢀor-
der:ꢀchemicalꢀshift,ꢀmultiplicityꢀ(sꢀ=ꢀsinglet,ꢀdꢀ=ꢀdoublet,ꢀtꢀ=ꢀ
triplet,ꢀmꢀ=ꢀmultiplet,ꢀbrꢀ=ꢀbroadꢀsignal),ꢀcouplingꢀconstantꢀ
inꢀhertzꢀ(Hz),ꢀandꢀsignalꢀareaꢀintegrationꢀinꢀnaturalꢀnum-
bers,ꢀ assignmentꢀ (italic).ꢀ High-resolutionꢀ massꢀ spectraꢀ
Compoundꢀ6.ꢀ1H-indane-1,3(2H)-dioneꢀ(4)ꢀwasꢀusedꢀasꢀ
aꢀnucleophile.ꢀTheꢀproductꢀ6ꢀwasꢀisolatedꢀbyꢀflashꢀchroma-
tographyꢀ(petroleumꢀether/ethylꢀacetateꢀ=ꢀ10/1)ꢀasꢀdeepꢀ
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
redꢀsolidꢀinꢀ56%ꢀyieldꢀ(46ꢀmg).ꢀMpꢀ>300ꢀ°C.ꢀ HꢀNMRꢀ(400ꢀ
MHz,ꢀCDCl )ꢀδꢀ9.07ꢀ(d,ꢀJꢀ=ꢀ7.8ꢀHz,ꢀ1H),ꢀ8.94ꢀ(s,ꢀ1H),ꢀ8.64ꢀ(s,ꢀ
3
(
HRMS)ꢀwereꢀobtainedꢀbyꢀESIꢀusingꢀaꢀtime-of-flightꢀmassꢀ
1H),ꢀ8.18ꢀ(d,ꢀJꢀ=ꢀ8.5ꢀHz,ꢀ1H),ꢀ8.04ꢀ(dd,ꢀJꢀ=ꢀ6.2,ꢀ3.6ꢀHz,ꢀ1H),ꢀ
7.94–7.84ꢀ(m,ꢀ3H),ꢀ7.84–7.74ꢀ(m,ꢀ2H),ꢀ7.72–7.63ꢀ(m,ꢀ1H),ꢀ
7.61–7.51ꢀ(m,ꢀ1H),ꢀ7.35ꢀ(dd,ꢀJꢀ=ꢀ6.4,ꢀ3.6ꢀHz,ꢀ2H),ꢀ5.19ꢀ(d,ꢀJꢀ=ꢀ
analyzerꢀonꢀaꢀBrukerꢀUltraꢀexTOF/TOFꢀspectrometer.ꢀUV-
VisꢀandꢀfluorescentꢀspectraꢀwereꢀrecordedꢀonꢀaꢀHitachiꢀU-
4
withꢀ 1ꢀ cmꢀ quartzꢀ cuvetteꢀ fromꢀ Starnaꢀ Cells,ꢀ Inc.ꢀ atꢀ roomꢀ
temperature.ꢀAbsoluteꢀfluorescentꢀquantumꢀyieldsꢀandꢀflu-
orescenceꢀlifetimesꢀatꢀroomꢀtemperatureꢀwereꢀdeterminedꢀ
byꢀ Quantaurus-QYꢀ C11347ꢀ (Hamamatsuꢀ Photonics)ꢀ andꢀ
Quantaurus-TauꢀC11367ꢀ(HamamatsuꢀPhotonics).ꢀ
13
1
100ꢀ andꢀ Hitachiꢀ F-7000ꢀ spectrophotometer,ꢀ equippedꢀ
1.7ꢀHz,ꢀ1H),ꢀ4.38ꢀ(d,ꢀJꢀ=ꢀ2.4ꢀHz,ꢀ1H).ꢀ C{ H}ꢀNMRꢀ(101ꢀMHz,ꢀ
CDCl )ꢀ δꢀ 202.6,ꢀ 199.0,ꢀ 197.5,ꢀ 142.6,ꢀ 142.2,ꢀ 141.9,ꢀ 135.8,ꢀ
3
135.5,ꢀ133.5,ꢀ133.3,ꢀ133.2,ꢀ131.7,ꢀ130.4,ꢀ129.5,ꢀ129.4,ꢀ128.8,ꢀ
128.4,ꢀ126.8,ꢀ126.7,ꢀ126.4,ꢀ126.2,ꢀ125.2,ꢀ125.0,ꢀ124.7,ꢀ123.6,ꢀ
+
ꢀ
123.4,ꢀ123.2,ꢀ55.3,ꢀ50.0.ꢀHRMSꢀ(ESI-TOF)ꢀm/z:ꢀ[M+H ]calcdꢀ
ꢀ413.1172,ꢀfoundꢀ413.1167.ꢀ
forꢀC29
H
17
O
3
ImprovedꢀSyntheticꢀProcedureꢀforꢀPreparationꢀofꢀtheꢀ
StartingꢀMaterialꢀ1.ꢀToꢀaꢀcoldꢀ(0ꢀ°C)ꢀstirredꢀsuspensionꢀofꢀ
tetraceneꢀ(500ꢀmg)ꢀinꢀortho-dichlorobenzeneꢀ(200ꢀmL)ꢀwasꢀ
addedꢀoxalylchlorideꢀ(615ꢀmg,ꢀ2.2ꢀequiv).ꢀToꢀtheꢀsuspensionꢀ
wasꢀthenꢀaddedꢀAlCl
inꢀ ortho-dichlorobenzeneꢀ (15ꢀ mL)ꢀ dropwise.ꢀ (Notice:ꢀ theꢀ
AlCl ꢀwasꢀaddedꢀinꢀthreeꢀtimesꢀinꢀ18ꢀh).ꢀTheꢀsuspensionꢀwasꢀ
warmedꢀtoꢀ25ꢀ°Cꢀandꢀstirredꢀforꢀanotherꢀ18ꢀh.ꢀTheꢀreactionꢀ
wasꢀstoppedꢀbyꢀadditionꢀofꢀ20ꢀmLꢀofꢀMeOH–aqueousꢀHClꢀ(1ꢀ
M)ꢀsolutionꢀ(9:1,ꢀv:v).ꢀTheꢀmixtureꢀwasꢀconcentratedꢀbyꢀus-
ingꢀanꢀevaporator.ꢀTheꢀprecipitateꢀwasꢀaddedꢀtoꢀ300ꢀmLꢀofꢀ
MeOH–aqueousꢀ HClꢀ (1ꢀ M)ꢀ solutionꢀ (9:1,ꢀ v:v)ꢀ andꢀ filteredꢀ
andꢀwashedꢀbyꢀMeOHꢀtoꢀgiveꢀtheꢀcrudeꢀproductꢀ(633ꢀmg),ꢀ
whichꢀwasꢀthenꢀsublimatedꢀunderꢀreducedꢀpressureꢀ(0.01ꢀ
MPa)ꢀatꢀ220ꢀ°Cꢀforꢀ15ꢀh.ꢀConsequently,ꢀtheꢀtitleꢀcompoundꢀ
wasꢀobtainedꢀasꢀaꢀblackꢀsolidꢀinꢀ52%ꢀyield.ꢀTheꢀproductꢀwasꢀ
Compoundꢀ6′.ꢀHantzschꢀesterꢀwasꢀabsenceꢀinꢀtheꢀsynthe-
sisꢀofꢀ6.ꢀTheꢀproductꢀ6′ꢀwasꢀisolatedꢀbyꢀflashꢀchromatog-
raphyꢀ(petroleumꢀether/ethylꢀacetateꢀ=ꢀ5/1)ꢀasꢀdeepꢀredꢀ
solidꢀinꢀ47%ꢀyieldꢀ(51ꢀmg)ꢀasꢀ6′+4.ꢀMpꢀ262–263ꢀ°C.ꢀThisꢀ
compoundꢀwasꢀobtainedꢀasꢀaꢀcomplexꢀwithꢀ4,ꢀwhichꢀwasꢀ
3
ꢀ(anhydrous,ꢀpowder,ꢀ1.17g,ꢀ4ꢀequiv)ꢀ
1
1
elucidatedꢀbyꢀ HꢀNMRꢀandꢀHRMS.ꢀ HꢀNMRꢀ(400ꢀMHz,ꢀCDCl )ꢀ
3
3
δꢀ9.02ꢀ(d,ꢀJꢀ=ꢀ8.7ꢀHz,ꢀ1H),ꢀ8.91ꢀ(s,ꢀ1H),ꢀ8.63ꢀ(s,ꢀ1H),ꢀ8.15ꢀ(dd,ꢀ
Jꢀ=ꢀ8.5ꢀandꢀ5.8ꢀHz,ꢀ2H),ꢀ7.96ꢀ(d,ꢀJꢀ=ꢀ8.5ꢀHz,ꢀ1H),ꢀ7.75ꢀ(br,ꢀ4H,ꢀ
C
6
H
4
),ꢀ7.68ꢀ(br,ꢀ4H,ꢀC
1H),ꢀ7.26ꢀ(t,ꢀ1H),ꢀ5.34ꢀ(s,ꢀ2H,ꢀCH
NMRꢀ(101ꢀMHz,ꢀCDCl )ꢀδꢀ(101ꢀMHz,ꢀCDCl
6
H ),ꢀ7.64ꢀ(t,ꢀ1H),ꢀ7.54ꢀ(t,ꢀ1H),ꢀ7.34ꢀ(t,ꢀ
4
ꢀ
13
1
2
ꢀofꢀindane-dione). C{ H}ꢀ
)ꢀδꢀ202.1,ꢀ197.2,ꢀ
3
3
197.1,ꢀ142.4,ꢀ142.4,ꢀ135.8,ꢀ135.4,ꢀ133.7,ꢀ133.6,ꢀ133.2,ꢀ132.0,ꢀ
130.9,ꢀ129.8,ꢀ129.5,ꢀ129.0,ꢀ127.9,ꢀ127.5,ꢀ126.7,ꢀ126.5,ꢀ126.4,ꢀ
125.8,ꢀ125.0,ꢀ124.9,ꢀ124.2,ꢀ123.3,ꢀ123.2,ꢀ60.4.ꢀHRMSꢀ(ESI-
+ ꢀ
TOF)ꢀ m/z:ꢀ [M+H ] calcdꢀ forꢀ C29
411.1017.ꢀ HRMSꢀ (ESI-TOF)ꢀ m/z:ꢀ [M(6′+4)+H ] calcdꢀ forꢀ
ꢀ557.1384,ꢀfoundꢀ557.1390.ꢀ
Compoundꢀ7.ꢀFollowingꢀtheꢀgeneralꢀprocedure,ꢀ1,3-di-
ethyl-2-thioxodihydropyrimidine-4,6(1H,5H)-dioneꢀ (5)ꢀ
H
15
O
3
ꢀ 411.1016,ꢀ foundꢀ
+
ꢀ
12
confirmedꢀwithꢀtheꢀspectralꢀdataꢀinꢀourꢀpreviousꢀpaper. ꢀ
C
38
H
21
O
5
Generalꢀ Proceduresꢀ forꢀ theꢀ Synthesisꢀ ofꢀ Reducedꢀ
Knoevenagelꢀproducts.ꢀAꢀdriedꢀSchlenkꢀtubeꢀwithꢀaꢀmag-
neticꢀstirꢀbarꢀwasꢀchargedꢀwithꢀcompoundꢀ1ꢀ(0.2ꢀmmol),ꢀnu-
cleophilesꢀ (0.24ꢀ mmol,ꢀ 1.2ꢀ equiv),ꢀ Hantzschꢀ esterꢀ (0.3ꢀ
mmol,ꢀ 1.5ꢀ equiv).ꢀ Theꢀ systemꢀ wasꢀ evacuatedꢀ thriceꢀ andꢀ
backfilledꢀwithꢀAr.ꢀNext,ꢀtheꢀsolventꢀDMSOꢀ(3.0ꢀmL)ꢀandꢀpi-
peridineꢀ(20.0ꢀmolꢀ%)ꢀwereꢀaddedꢀviaꢀaꢀsyringe.ꢀThen,ꢀtheꢀ
reactionꢀmixtureꢀwasꢀstirredꢀatꢀ60ꢀ°Cꢀforꢀ8ꢀhꢀinꢀanꢀoilꢀbath.ꢀ
Afterꢀtheꢀreactionꢀmixtureꢀwasꢀcooledꢀtoꢀambientꢀtempera-
ture,ꢀtheꢀreactionꢀwasꢀquenchedꢀwithꢀaqueousꢀHClꢀ(0.1ꢀM)ꢀ
solutionꢀ (1ꢀ mL)ꢀ andꢀ extractedꢀ withꢀ dichloromethaneꢀ (10ꢀ
wasꢀusedꢀasꢀaꢀnucleophile.ꢀTheꢀproductꢀ7ꢀwasꢀisolatedꢀbyꢀ
flashꢀchromatographyꢀ(ethylꢀacetate/MeOHꢀ=ꢀ20/1)ꢀasꢀdeepꢀ
1
redꢀsolidꢀinꢀ74%ꢀyieldꢀ(71ꢀmg).ꢀMpꢀ>300ꢀ°C.ꢀ HꢀNMRꢀ(400ꢀ
MHz,ꢀCDCl )ꢀδꢀ9.17ꢀ(dd,ꢀJꢀ=ꢀ8.7,ꢀ0.9ꢀHz,ꢀ1H),ꢀ8.95ꢀ(s,ꢀ1H),ꢀ8.67ꢀ
3
(s,ꢀ1H),ꢀ8.19ꢀ(d,ꢀJꢀ=ꢀ8.8ꢀHz,ꢀ1H),ꢀ8.07ꢀ(dd,ꢀJꢀ=ꢀ5.7,ꢀ4.2ꢀHz,ꢀ1H),ꢀ
7.77–7.69ꢀ(m,ꢀ2H),ꢀ7.63–7.56ꢀ(m,ꢀ1H),ꢀ7.46–7.38ꢀ(m,ꢀ2H),ꢀ
5.34ꢀ(d,ꢀJꢀ=ꢀ1.1ꢀHz,ꢀ1H),ꢀ4.86ꢀ(d,ꢀJꢀ=ꢀ2.1ꢀHz,ꢀ1H),ꢀ4.53–4.43ꢀ(m,ꢀ
1H),ꢀ4.39ꢀ(dd,ꢀJꢀ=ꢀ13.1,ꢀ7.0ꢀHz,ꢀ1H),ꢀ4.27–4.12ꢀ(m,ꢀ2H),ꢀ1.24ꢀ
13
(t,ꢀJꢀ=ꢀ7.0ꢀHz,ꢀ3H),ꢀ0.82ꢀ(t,ꢀJꢀ=ꢀ6.9ꢀHz,ꢀ3H).ꢀ CꢀNMRꢀ(101ꢀMHz,ꢀ
CDCl )ꢀ δꢀ 201.7,ꢀ 179.1,ꢀ 165.9,ꢀ 164.2,ꢀ 141.8,ꢀ 133.4,ꢀ 133.2,ꢀ
mLꢀxꢀ3).ꢀTheꢀorganicꢀphaseꢀwasꢀdriedꢀwithꢀNa
2
4
SO ꢀandꢀtheꢀ
3
solventꢀ wasꢀ removedꢀ underꢀ reduceꢀ pressure.ꢀ Theꢀ crudeꢀ
mixtureꢀwasꢀpurifiedꢀbyꢀsilicaꢀgelꢀflashꢀchromatographyꢀtoꢀ
giveꢀtheꢀpureꢀproduct.ꢀ
130.9,ꢀ130.6,ꢀ129.7,ꢀ129.4,ꢀ128.9,ꢀ127.2,ꢀ126.8,ꢀ126.6,ꢀ126.4,ꢀ
126.4,ꢀ125.2,ꢀ124.6,ꢀ123.1,ꢀ52.5,ꢀ51.2,ꢀ43.9,ꢀ43.4,ꢀ12.1,ꢀ11.7.ꢀ
+ ꢀ
HRMSꢀ (ESI-TOF)ꢀ m/z:ꢀ [M+H ] calcdꢀ forꢀ C28
H
23
O
3
2
N Sꢀ
467.1424,ꢀfoundꢀ467.1420.ꢀ
Compoundꢀ3.ꢀFollowingꢀtheꢀgeneralꢀprocedure,ꢀ3-ethyl-
rhodanineꢀwasꢀusedꢀasꢀaꢀnucleophile.ꢀTheꢀreactionꢀwasꢀcar-
riedꢀoutꢀatꢀ90ꢀ°Cꢀforꢀ4ꢀh.ꢀTheꢀproductꢀ3ꢀwasꢀisolatedꢀbyꢀflashꢀ
chromatographyꢀ(petroleumꢀether/ethylꢀacetateꢀ=ꢀ10/1)ꢀasꢀ
deepꢀredꢀsolidꢀinꢀ42%ꢀyieldꢀ(36ꢀmg).ꢀMpꢀ266–270ꢀ°C.ꢀ Hꢀ
NMRꢀ(400ꢀMHz,ꢀCDCl
Synthesisꢀofꢀcompoundꢀ6ꢀfromꢀtheꢀintermediateꢀ6′.ꢀAꢀ
driedꢀSchlenkꢀtubeꢀwithꢀaꢀmagneticꢀstirꢀbarꢀwasꢀ chargedꢀ
withꢀcompoundꢀ6′ꢀ(0.02ꢀmmol),ꢀHantzschꢀesterꢀ(5ꢀmg,ꢀ1.0ꢀ
equiv).ꢀTheꢀsystemꢀwasꢀevacuatedꢀthriceꢀandꢀbackfilledꢀwithꢀ
Ar.ꢀNext,ꢀtheꢀsolventꢀDMSOꢀ(1.0ꢀmL)ꢀandꢀpiperidineꢀ(10ꢀmolꢀ
%)ꢀ wereꢀ addedꢀ viaꢀ aꢀ syringe.ꢀ Then,ꢀ theꢀ reactionꢀ mixtureꢀ
1
3
)ꢀδꢀ9.06ꢀ(d,ꢀJꢀ=ꢀ8.7ꢀHz,ꢀ1H),ꢀ8.91ꢀ(s,ꢀ1H),ꢀ
8
.67ꢀ(s,ꢀ1H),ꢀ8.16ꢀ(d,ꢀJꢀ=ꢀ8.6ꢀHz,ꢀ1H),ꢀ8.11ꢀ(d,ꢀJꢀ=ꢀ8.7ꢀHz,ꢀ1H),ꢀ
ACS Paragon Plus Environment

The Journal of Organic Chemistry
wasꢀstirredꢀatꢀ60ꢀ°Cꢀforꢀ1ꢀhꢀinꢀanꢀoilꢀbath.ꢀAfterꢀtheꢀreactionꢀ
REFERENCES
Page 6 of 7
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
mixtureꢀwasꢀcooledꢀtoꢀambientꢀtemperature,ꢀtheꢀreactionꢀ
wasꢀquenchedꢀwithꢀaqueousꢀHClꢀ(0.1ꢀM)ꢀsolutionꢀ(1ꢀmL)ꢀ
andꢀextractedꢀwithꢀdichloromethaneꢀ(10ꢀmLꢀxꢀ3).ꢀTheꢀor-
(
1) Chaolumen;ꢀMurata,ꢀM.;ꢀSugano,ꢀY.;ꢀWakamiya,ꢀA.;ꢀMurata,ꢀY.ꢀ
Electron-DeficientꢀTetrabenzo-FusedꢀPyracyleneꢀandꢀConver-
sionsꢀintoꢀCurvedꢀandꢀPlanarꢀp-SystemsꢀHavingꢀDistinctꢀEmis-
sionꢀBehaviors.ꢀAngew.ꢀChem.ꢀInt.ꢀEd.ꢀ2015,ꢀ54,ꢀ9308–9312.ꢀ
(b)ꢀ Wombacher,ꢀ T.;ꢀ Gassmann,ꢀ A.;ꢀ Foro,ꢀ S.ꢀ vonꢀ Seggern,ꢀ H.;ꢀ
Schneider,ꢀJ.ꢀJ.ꢀStructuralꢀPolymorphismꢀandꢀThinꢀFilmꢀTran-
sistorꢀ Behaviorꢀ inꢀ theꢀ Fullereneꢀ Frameworkꢀ Moleculeꢀ
ganicꢀphaseꢀwasꢀdriedꢀwithꢀNa
2
SO ꢀandꢀtheꢀsolventꢀwasꢀre-
4
movedꢀunderꢀreduceꢀpressure.ꢀTheꢀcrudeꢀmixtureꢀwasꢀpuri-
fiedꢀ byꢀ silicaꢀ gelꢀ flashꢀ chromatographyꢀ toꢀ giveꢀ theꢀ pureꢀ
product.ꢀ
5
,6;11,12-di-o-Phenylenetetracene.ꢀ Angew.ꢀ Chem.ꢀ Int.ꢀ Ed.ꢀ
Electrochemicalꢀ measurements.ꢀ Cyclicꢀ voltammetryꢀ
andꢀdifferentialꢀpulseꢀvoltammetryꢀwereꢀperformedꢀusingꢀ
CHI660Eꢀ voltammetricꢀ analyzer.ꢀ Allꢀ measurementsꢀ wereꢀ
carriedꢀ outꢀ inꢀ aꢀ one-compartmentꢀ cellꢀ underꢀ argonꢀ gas,ꢀ
equippedꢀ withꢀ aꢀ platinumꢀ workingꢀ electrode,ꢀ aꢀ platinumꢀ
wireꢀcounterꢀelectrode,ꢀandꢀanꢀAg/Ag ꢀreferenceꢀelectrode.ꢀ
Theꢀ supportingꢀ electrolyteꢀ wasꢀ aꢀ 0.1ꢀ mol/Lꢀ dichloro-
methaneꢀsolutionꢀofꢀtetrabutylammoniumꢀhexafluorophos-
2016,ꢀ55,ꢀ6041ꢀ–6046.ꢀ(c)ꢀChaolumen;ꢀMurata,ꢀM.;ꢀWakamiya,ꢀ
A.;ꢀMurata,ꢀY.ꢀDithieno-FusedꢀPolycyclicꢀAromaticꢀHydrocar-
bonꢀwithꢀaꢀPyracyleneꢀMoiety:ꢀStrongꢀAntiaromaticꢀContribu-
tionꢀtoꢀtheꢀElectronicꢀStructure.ꢀOrg.ꢀLett.ꢀ2017,ꢀ19,ꢀ826–829.ꢀ
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(
d)ꢀChaolumen;ꢀMurata,ꢀM.;ꢀWakamiya,ꢀA.;ꢀMurata,ꢀY.ꢀUnsym-
+
metricꢀ Twofoldꢀ Schollꢀ Cyclizationꢀ ofꢀ aꢀ 5,11-Dinaphthyl-te-
tracene:ꢀ Selectiveꢀ Formationꢀ ofꢀ Pentagonalꢀ andꢀ Hexagonalꢀ
Ringsꢀ viaꢀ Dicationicꢀ Intermediates.ꢀ Angew.ꢀ Chem.ꢀ Int.ꢀ Ed.ꢀ
2
017,ꢀ56,ꢀ5082–5086.ꢀ
phateꢀ(TBAPF ).ꢀ
6
(
2) (a)ꢀClar,ꢀE.;ꢀWillicks,ꢀW.ꢀErichꢀClarꢀundꢀWinfriedꢀWillicks:ꢀAror-
natischeꢀ Kohlenwasser-stoffe,ꢀ LXIX.ꢀ Mitteil.:ꢀ 7.8;16.16-
Dibenzterrylen.ꢀChem.ꢀBer.ꢀ1955,ꢀ88,ꢀ1205–1207.ꢀ(b)ꢀAvlase-
vich,ꢀ Y.;ꢀ Mullen,ꢀ K.ꢀ Dibenzopentarylenebis(dicarboximide)s:ꢀ
NovelꢀNear-infraredꢀAbsorbingꢀDyes.ꢀChem.ꢀCommun.ꢀ2006,ꢀ
Computationalꢀ calculation.ꢀ Allꢀ calculationsꢀ wereꢀ car-
riedꢀoutꢀbyꢀusingꢀGaussian09ꢀpackageꢀatꢀtheꢀB3LYP.ꢀAꢀ6-
31G(d)ꢀbasisꢀsetꢀwasꢀusedꢀforꢀeachꢀlevel.ꢀTheꢀcalculationꢀlev-
elsꢀareꢀdescribedꢀasꢀ"B3LYP/ꢀ6-31G(d)".ꢀ
4
440–4442.ꢀ(c)ꢀKatsuta,ꢀS.;ꢀTanaka,ꢀK.;ꢀMaruya,ꢀY.;ꢀMori,ꢀS.;ꢀ
SCLCꢀmeasurements.ꢀTheꢀmobilityꢀwasꢀdeterminedꢀbyꢀ
Masuo,ꢀS.;ꢀOkujima,ꢀT.;ꢀUno,ꢀH.;ꢀNakayama,ꢀK.;ꢀYamada,ꢀH.ꢀSyn-
thesisꢀ ofꢀ Pentacene-,ꢀ Tetracene-ꢀ andꢀ Anthraceneꢀ Bisimidesꢀ
UsingꢀDouble-cyclizationꢀReactionꢀMediatedꢀbyꢀBismuthꢀ(III)ꢀ
Triflate.ꢀChem.ꢀCommun.ꢀ2011,ꢀ47,ꢀ10112–10114.ꢀ(d)ꢀYue,ꢀW.;ꢀ
Gao,ꢀJ.;ꢀLi,ꢀY.;ꢀJiang,ꢀW.;ꢀMotta,ꢀS.ꢀD.;ꢀNegri,ꢀF.;ꢀWang,ꢀZ.ꢀOne-Potꢀ
SynthesisꢀofꢀStableꢀNIRꢀTetraceneꢀDiimidesꢀviaꢀDoubleꢀCross-
Coupling.ꢀJ.ꢀAm.ꢀChem.ꢀSoc.ꢀ2011,ꢀ133,ꢀ18054–18057.ꢀ(e)ꢀCha-
olumen;ꢀ Enno,ꢀ H.;ꢀ Murata,ꢀ M.;ꢀ Wakamiya,ꢀ A.;ꢀ Murata,ꢀ Y.ꢀ
Dibenzo[a,f]peryleneꢀ Bisimide:ꢀ Effectsꢀ ofꢀ Introducingꢀ Twoꢀ
Fusedꢀ Rings.ꢀ Chem.ꢀ Asianꢀ J.ꢀ 2014,ꢀ 9,ꢀ 3136–3140.ꢀ (f)ꢀ Ajaya-
kumar,ꢀ M.ꢀ R.;ꢀ Fu,ꢀ Y.;ꢀ Ma,ꢀ J.;ꢀ Hennersdorf,ꢀ F.;ꢀ Komber,ꢀ H.;ꢀ
Weigand,ꢀ J.ꢀ J.;ꢀ Alfonsov,ꢀ A.;ꢀ Popov,ꢀ A.ꢀ A.;ꢀ Berger,ꢀ R.;ꢀ Liu,ꢀ J.;ꢀ
fittingꢀtheꢀdarkꢀcurrentꢀtoꢀaꢀmodelꢀofꢀaꢀsingle-carrierꢀSCLC,ꢀ
ꢉ
ꢂ
ꢈ
whichꢀisꢀdescribedꢀbyꢀtheꢀequation:ꢀꢁ = ꢄ ꢄ ꢇ ꢊꢋ,ꢀwhereꢀJꢀisꢀ
ꢅ
ꢆ
ꢃ
theꢀcurrentꢀdensity,ꢀµꢀisꢀtheꢀmobility,ꢀε
0
ꢀisꢀtheꢀpermittivityꢀ
ofꢀfreeꢀspace,ꢀε ꢀisꢀtheꢀrelativeꢀpermittivityꢀofꢀtheꢀmaterial,ꢀLꢀ
r
isꢀtheꢀthicknessꢀofꢀtheꢀtetraceneꢀderivativeꢀlayer,ꢀandꢀVꢀisꢀtheꢀ
effectiveꢀvoltage.ꢀTheꢀthicknessꢀofꢀtheꢀthinꢀfilmsꢀwasꢀmeas-
uredꢀwithꢀaꢀDEKTAKꢀ6Mꢀstylusꢀprofilometer.ꢀAꢀsolutionꢀofꢀ
tetraceneꢀderivativeꢀwasꢀspin-coatedꢀontoꢀtheꢀAl/glassꢀtoꢀ
formꢀ aꢀ thinꢀ filmꢀ inꢀ electron-onlyꢀ devices,ꢀ andꢀ ontoꢀ theꢀ
PEDOT:PSSꢀinꢀhole-onlyꢀdevices.ꢀTheꢀLiF/Alꢀelectrodesꢀ(LiFꢀ
Mu ̈l len,ꢀ K.;ꢀ Feng,ꢀ X.ꢀ Towardꢀ Fullꢀ Zigzag-Edgedꢀ Nanogra-
=
ꢀ0.6ꢀnm;ꢀAlꢀ=ꢀ100ꢀnm)ꢀorꢀMoO /Alꢀwereꢀevaporatedꢀontoꢀ
3
phenes:ꢀperi-TetraceneꢀandꢀItsꢀCorrespondingꢀCircumanthra-
cene.ꢀJ.ꢀAm.ꢀChem.ꢀSoc.ꢀ2018,ꢀ140,ꢀ6240−6244.ꢀ(g)ꢀNi,ꢀY.;ꢀGopa-
lakrishna,ꢀT.ꢀY.;ꢀPhan,ꢀH.;ꢀHerng,ꢀT.ꢀS.;ꢀWu,ꢀS.;ꢀHan,ꢀY.;ꢀDing,ꢀJ.;ꢀ
Wu,ꢀJ.-S.ꢀAꢀPeri-tetraceneꢀDiradicaloid:ꢀSynthesisꢀandꢀProper-
ties.ꢀAngew.ꢀChem.ꢀInt.ꢀEd.ꢀ2018,ꢀ57,ꢀ9697–9701.ꢀ
theꢀtetraceneꢀderivativeꢀthinꢀfilmsꢀinꢀtheꢀelectron-onlyꢀde-
vicesꢀandꢀhole-onlyꢀdevices,ꢀrespectively.ꢀTheꢀexperimentalꢀ
darkꢀcurrentꢀdensityꢀJꢀwasꢀmeasuredꢀunderꢀanꢀappliedꢀvolt-
ageꢀsweptꢀfromꢀ–5ꢀtoꢀ5ꢀV.ꢀ
(
3) (a)ꢀYin,ꢀJ.;ꢀZhang,ꢀK.;ꢀJiao,ꢀC.;ꢀLi,ꢀJ.;ꢀChi,ꢀC.;ꢀWu,ꢀJ.-S.ꢀSynthesisꢀofꢀ
Functionalizedꢀ Tetraceneꢀ Dicarboxylicꢀ Imides.ꢀ Tetrahedronꢀ
Lett.ꢀ2010,ꢀ51,ꢀ6313–6315.ꢀ(b)ꢀNakagawa,ꢀT.;ꢀSuzuki,ꢀT.;ꢀKö-
nig,ꢀM.;ꢀGuldi,ꢀD.ꢀM.;ꢀMatsuo,ꢀY.ꢀSynthesis,ꢀPhotophysicalꢀProp-
erties,ꢀandꢀExcitedꢀStateꢀDynamicsꢀofꢀaꢀPlatinumꢀComplexꢀofꢀ
TetraceneꢀImideꢀDisulfide.ꢀChem.ꢀCommun.ꢀ2013,ꢀ49,ꢀ10394–
ASSOCIATED CONTENT
Supporting Information
Improvedꢀproceduresꢀforꢀsynthesisꢀofꢀtheꢀstartingꢀmaterialꢀ1,ꢀ
1
13
Hꢀandꢀ CꢀNMRꢀspectra,ꢀandꢀHRMS,ꢀthermalꢀstability,ꢀfluores-
1
0396.ꢀ(c)ꢀSuzuki,ꢀT.;ꢀNakagawa,ꢀT.;ꢀOhkubo,ꢀK.;ꢀFukuzumi,ꢀS.;ꢀ
cence,ꢀ computationalꢀ calculation,ꢀ SCLCꢀ measurementsꢀ data.ꢀ
Thisꢀ materialꢀ isꢀ availableꢀ freeꢀ ofꢀ chargeꢀ viaꢀ theꢀ Internetꢀ atꢀ
http://pubs.acs.org.ꢀ
Matsuo,ꢀY.ꢀElectronicꢀInfraredꢀLightꢀAbsorptionꢀofꢀaꢀtri-Palla-
diumꢀ Complexꢀ Containingꢀ Twoꢀ p–Expandedꢀ Tetraceneꢀ Lig-
ands.ꢀChem.ꢀSci.ꢀ2014,ꢀ5,ꢀ4888–4894.ꢀ
(
4) (a)ꢀReichwagen,ꢀJ.;ꢀHopf,ꢀH.;ꢀGuerzo,ꢀA.ꢀD.;ꢀBelin,ꢀC.;ꢀDesvergne,ꢀ
J.ꢀ P.;ꢀ Bouas-Laurent,ꢀ H.ꢀ Synthesisꢀ ofꢀ 2,3-Substitutedꢀ Te-
tracenesꢀandꢀEvaluationꢀofꢀTheirꢀSelf-AssemblingꢀPropertiesꢀ
inꢀOrganicꢀSolvents.ꢀOrg.ꢀLett.ꢀ2005,ꢀ7,ꢀ971–974.ꢀ(b)ꢀPapagni,ꢀ
A.;ꢀTrombini,ꢀC.;ꢀLombardo,ꢀM.;ꢀBergantin,ꢀS.;ꢀChams,ꢀA.;ꢀChi-
arucci,ꢀM.;ꢀMiozzo,ꢀL.;ꢀParravicini,ꢀM.ꢀCross-Couplingꢀofꢀ5,11-
Dibromotetraceneꢀ Catalyzedꢀ byꢀ aꢀ Triethylammoniumꢀ Ionꢀ
TaggedꢀDiphenylphosphineꢀPalladiumꢀComplexꢀinꢀIonicꢀLiq-
uids.ꢀ Organometallicsꢀ 2011,ꢀ 30,ꢀ 4325–4329.ꢀ (c)ꢀ Huang,ꢀ Z.;ꢀ
Simpson,ꢀ D.ꢀ E.;ꢀ Mahboub,ꢀ M.;ꢀ Li,ꢀ X.;ꢀ Tang,ꢀ M.-L.ꢀ Ligandꢀ En-
hancedꢀ Upconversionꢀ ofꢀ Near-infraredꢀ Photonsꢀ withꢀ Nano-
crystalꢀLightꢀAbsorbers.ꢀChem.ꢀSci.ꢀ2016,ꢀ7,ꢀ4101–4104.ꢀ(d)ꢀ
Wombacher,ꢀT.;ꢀGoddard,ꢀR.;ꢀLehmann,ꢀC.ꢀW.;ꢀSchneider,ꢀJ.ꢀJ.ꢀ
Organometallicꢀ Rubidiumꢀ andꢀ Cesiumꢀ Compoundsꢀ ofꢀ Theꢀ
5,6;11,12-di-o-phenylene-tetraceneꢀDianion.ꢀChem.ꢀCommun.ꢀ
AUTHOR INFORMATION
Corresponding Author
*ꢀE-mail:ꢀmatsuo@ustc.edu.cn;ꢀmatsuo@photon.t.u-tokyo.ac.jpꢀ
Notes
Theꢀauthorsꢀdeclareꢀnoꢀcompetingꢀfinancialꢀinterest.ꢀ
ACKNOWLEDGMENT
Thisꢀ workꢀ wasꢀ supportedꢀ byꢀ theꢀ high-levelꢀ humanꢀ resourceꢀ
fundingꢀinꢀUniversityꢀofꢀScienceꢀandꢀTechnologyꢀofꢀChina.ꢀPartꢀ
ofꢀworkꢀwasꢀfinanciallyꢀsupportedꢀbyꢀGrants-in-AidꢀforꢀScien-
tificꢀ Researchꢀ (JSPSꢀ KAKENHIꢀ Grantꢀ Numbersꢀ JP15H05760,ꢀ
JP16H04187,ꢀandꢀJP17K19116),ꢀtheꢀMinistryꢀofꢀEducation,ꢀCul-
ture,ꢀSports,ꢀScienceꢀandꢀTechnologyꢀ(MEXT),ꢀJapan.ꢀꢀ
2
017,ꢀ53,ꢀ7030–7033.ꢀ(e)ꢀLi,ꢀX.;ꢀFast,ꢀA.;ꢀHuang,ꢀZ.;ꢀFishman,ꢀ
D.ꢀA.;ꢀTang,ꢀM.-L.ꢀPbS/CdSꢀCore–ShellꢀQuantumꢀDotsꢀSuppressꢀ
ACS Paragon Plus Environment

Page 7 of 7
The Journal of Organic Chemistry
ChargeꢀTransferꢀandꢀEnhanceꢀTripletꢀTransfer.ꢀAngew.ꢀChem.ꢀ
SlippedꢀStackedꢀStructure.ꢀJ.ꢀPhotochem.ꢀPhotobiol.ꢀ2017,ꢀ340,ꢀ
1
2
3
4
5
6
7
8
9
Int.ꢀEd.ꢀ2017,ꢀ56,ꢀ5598–5602.ꢀ
21–28.ꢀ
(
5) (a)ꢀMoon,ꢀH.;ꢀZeis,ꢀR.;ꢀBorkent,ꢀE.ꢀJ.ꢀBesnard,ꢀC.;ꢀLovinger,ꢀA.ꢀJ.;ꢀ
Siegrist,ꢀKloc,ꢀT.ꢀC.ꢀBao,ꢀZ.-N.ꢀSynthesis,ꢀCrystalꢀStructure,ꢀandꢀ
TransistorꢀPerformanceꢀofꢀTetraceneꢀDerivatives.ꢀJ.ꢀAm.ꢀChem.ꢀ
Soc.ꢀ 2004,ꢀ 126,ꢀ 15322–15323.ꢀ (b)ꢀ Kojima,ꢀ S.;ꢀ Okamoto,ꢀ T.;ꢀ
Miwa,ꢀK.;ꢀSato,ꢀH.;ꢀTakeya,ꢀJ.;ꢀMatsuo,ꢀY.ꢀBenzopyrazine-fusedꢀ
TetraceneꢀDerivatives:ꢀThin-filmꢀFormationꢀatꢀtheꢀCrystallineꢀ
Mesophaseꢀ forꢀ Solution-processedꢀ Holeꢀ Transportingꢀ De-
vices.ꢀOrg.ꢀElectron.ꢀ2013,ꢀ14,ꢀ437–444.ꢀ(c)ꢀSuzuki,ꢀT.;ꢀOka-
moto,ꢀT.;ꢀSaeki,ꢀA.;ꢀSeki,ꢀS.;ꢀSato,ꢀH.;ꢀMatsuo,ꢀY.ꢀFormationꢀofꢀ
PhotoconductiveꢀNanowiresꢀofꢀTetraceneꢀDerivativeꢀinꢀCom-
positeꢀThinꢀFilm.ꢀACSꢀAppl.ꢀMater.ꢀInterfacesꢀ2013,ꢀ5,ꢀ1937–
1942.ꢀ(d)ꢀXu,ꢀW.;ꢀHe,ꢀY.;ꢀMurtaza,ꢀI.;ꢀZhang,ꢀD.;ꢀLi,ꢀA.;ꢀHu,ꢀZ.;ꢀ
Zeng,ꢀX.;ꢀGuo,ꢀY.;ꢀZhu,ꢀY.;ꢀLiu,ꢀM.;ꢀMeng,ꢀH.ꢀPhenylꢀSubstitutionꢀ
inꢀTetracene:ꢀaꢀPromisingꢀStrategyꢀtoꢀBoostꢀChargeꢀMobilityꢀ
inꢀ Thinꢀ Filmꢀ Transistors.ꢀ J.ꢀ Mater.ꢀ Chem.ꢀ Cꢀ 2017,ꢀ 5,ꢀ 2852–
(9) Shandura,ꢀM.ꢀP.;ꢀPoronik,ꢀY.ꢀM.;ꢀKovtun,ꢀY.ꢀP.;ꢀIshchenko,ꢀA.ꢀA.ꢀ
SubstitutedꢀXanthylocyanines,ꢀPartꢀIV:ꢀTrinuclearꢀDyesꢀwithꢀaꢀ
PyronineꢀNucleus.ꢀDyesꢀandꢀPigmentsꢀ2008,ꢀ77,ꢀ369–373.ꢀ
(10) Li,ꢀZ.;ꢀHe,ꢀG.;ꢀWan,ꢀX.;ꢀLiu,ꢀY.;ꢀZhou,ꢀJ.;ꢀLong,ꢀG.;ꢀZuo,ꢀY.;ꢀZhang,ꢀ
M.;ꢀChen,ꢀY.-S.ꢀSolutionꢀProcessableꢀRhodanine-BasedꢀSmallꢀ
MoleculeꢀOrganicꢀPhotovoltaicꢀCellsꢀwithꢀaꢀPowerꢀConversionꢀ
Efficiencyꢀofꢀ6.1%ꢀAdv.ꢀEnergyꢀMater.ꢀ2012,ꢀ2,ꢀ74–77.ꢀ
(11) (a)ꢀ Kim,ꢀ Y.;ꢀ Song,ꢀ C.ꢀ E.;ꢀ Moon,ꢀ S.ꢀ J.;ꢀ Lim,ꢀ E.ꢀRhodanineꢀ Dye-
basedꢀ Smallꢀ Moleculeꢀ Acceptorsꢀ forꢀ Organicꢀ Photovoltaicꢀ
Cells.ꢀChem.ꢀCommun.ꢀ2014,ꢀ50,ꢀ8235–8238.ꢀ(b)ꢀHolliday,ꢀS.;ꢀ
Ashraf,ꢀR.ꢀS.;ꢀNielsen,ꢀC.ꢀB.;ꢀKirkus,ꢀM.;ꢀRohr,ꢀJ.ꢀA.;ꢀTan,ꢀC.-H.;ꢀ
Collado-Fregoso,ꢀ E.;ꢀ Knall,ꢀ A.ꢀ C.;ꢀ Durrant,ꢀ J.ꢀ R.;ꢀ Nelson,ꢀ J.;ꢀ
McCulloch,ꢀI.ꢀAꢀRhodanineꢀFlankedꢀNonfullereneꢀAcceptorꢀforꢀ
Solution-Processedꢀ Organicꢀ Photovoltaics.ꢀ J.ꢀ Am.ꢀ Chem.ꢀ Soc.ꢀ
2015,ꢀ137,ꢀ898–904.ꢀ
(12) Okamoto,ꢀT.;ꢀSuzuki,ꢀT.;ꢀKojima,ꢀS.;ꢀMatsuo,ꢀY.ꢀSynthesis,ꢀPhys-
icalꢀProperties,ꢀandꢀCrystalꢀStructureꢀofꢀAcetetracenylene-1,2-
dione.ꢀChem.ꢀLett.ꢀ2011,ꢀ40,ꢀ739–741.ꢀ
(13) Ramachary,ꢀ D.ꢀ B.;ꢀ Kishor,ꢀ M.;ꢀ Reddy,ꢀ Y.ꢀ V.ꢀ Developmentꢀ ofꢀ
Pharmaceuticalꢀ Drugs,ꢀ Drugꢀ Intermediatesꢀ andꢀ Ingredientsꢀ
byꢀ Usingꢀ Directꢀ Organo-Clickꢀ Reactions.ꢀ Eur.ꢀ J.ꢀ Org.ꢀ Chem.ꢀ
2008,ꢀ975–993.ꢀ
(14) (a)ꢀKosower,ꢀE.ꢀM.ꢀIntramolecularꢀDonor-AcceptorꢀSystems.ꢀ9.ꢀ
Photophysicsꢀofꢀ(Phenylamino)naphthalenesulfonates:ꢀAꢀPar-
adigmꢀforꢀExcited-StateꢀIntramolecularꢀChargeꢀTransfer.ꢀAcc.ꢀ
Chem.ꢀRes.ꢀ1982,ꢀ15,ꢀ259–266.ꢀ(b)ꢀGrabowski,ꢀZ.ꢀR.;ꢀRotkie-
wicz,ꢀK.;ꢀRettig,ꢀW.ꢀStructuralꢀChangesꢀAccompanyingꢀIntra-
molecularꢀElectronꢀTransfer:ꢌꢀFocusꢀonꢀTwistedꢀIntramolecu-
larꢀCharge-TransferꢀStatesꢀandꢀStructures.ꢀChem.ꢀRev.ꢀ2003,ꢀ
103,ꢀ3899–4031.ꢀ
(15) Il’ichev,ꢀ Y.ꢀ V.;ꢀ Kühnle,ꢀ W.;ꢀ Zachariasse,ꢀ K.ꢀ A.ꢀ Intramolecularꢀ
ChargeꢀTransferꢀinꢀDualꢀFluorescentꢀ4-(Dialkylamino)ꢀbezoni-
triles.ꢀReactionꢀEfficiencyꢀEnhancementꢀbyꢀIncreasingꢀtheꢀSizeꢀ
ofꢀtheꢀAminoꢀandꢀBenzonitrileꢀSubunitsꢀbyꢀAlkylꢀSubstituents.ꢀ
J.ꢀPhys.ꢀChem.ꢀAꢀ1998,ꢀ102,ꢀ5670–5680.ꢀ
(16) Matsuo,ꢀY.;ꢀIwashita,ꢀA.;ꢀAbe,ꢀY.;ꢀLi,ꢀC.-Z.;ꢀMatsuo,ꢀK.;ꢀHashigu-
chi,ꢀ M.;ꢀ Nakamura,ꢀ E.ꢀ Regioselectiveꢀ Synthesisꢀ ofꢀ 1,4-Di(or-
gano)[60]fullerenesꢀ throughꢀ DMF-assistedꢀ Monoadditionꢀ ofꢀ
SilylmethylꢀGrignardꢀReagentsꢀandꢀSubsequentꢀAlkylationꢀRe-
action.ꢀJ.ꢀAm.ꢀChem.ꢀSoc.ꢀ2008,ꢀ130,ꢀ15429–15436.ꢀ
(17) Blom,ꢀP.ꢀW.ꢀM.;ꢀdeꢀJong,ꢀM.ꢀJ.ꢀM.;ꢀVleggaar,ꢀJ.ꢀJ.ꢀM.ꢀElectronꢀandꢀ
HoleꢀTransportꢀinꢀPoly(p-phenyleneꢀvinylene)ꢀDevices.ꢀAppl.ꢀ
Phys.ꢀLett.ꢀ1996,ꢀ68,ꢀ3308.ꢀ
(18) Kumar,ꢀC.ꢀV.;ꢀCabau,ꢀL.;ꢀKoukaras,ꢀE.ꢀN.;ꢀSharma,ꢀA.;ꢀSharma,ꢀG.ꢀ
D.;ꢀ Palomares,ꢀ E.ꢀ A–p–D–p–Aꢀ Basedꢀ Porphyrinꢀ forꢀ Solutionꢀ
ProcessedꢀSmallꢀMoleculeꢀBulkꢀHeterojunctionꢀSolarꢀCells.ꢀJ.ꢀ
Mater.ꢀChem.ꢀAꢀ2015,ꢀ3,ꢀ16287–16301.ꢀ
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2
858.ꢀ(e)ꢀPurvis,ꢀL.ꢀJ.;ꢀGu,ꢀX.;ꢀGhosh,ꢀS.;ꢀZhang,ꢀZ.;ꢀCramer,ꢀC.ꢀJ.;ꢀ
Douglas,ꢀ C.ꢀ J.ꢀ Synthesisꢀ andꢀ Characterizationꢀ ofꢀ Electron-
Deficientꢀ Asymmetricallyꢀ Substitutedꢀ Diarylin-
denotetracenes.ꢀJ.ꢀOrg.ꢀChem.ꢀ2018,ꢀ83,ꢀ1828−1841.ꢀ
(
6) Okamoto,ꢀT.;ꢀSuzuki,ꢀT.;ꢀTanaka,ꢀH.;ꢀHashizume,ꢀD.;ꢀMatsuo,ꢀY.ꢀ
TetraceneꢀDicarboxylicꢀImideꢀandꢀItsꢀDisulfide:ꢀSynthesisꢀofꢀ
AmbipolarꢀOrganicꢀSemiconductorsꢀforꢀOrganicꢀPhotovoltaicꢀ
Cells.ꢀChem.ꢀAsianꢀJ.ꢀ2012,ꢀ7,ꢀ105–111.ꢀ
(7) (a)ꢀMuller,ꢀA.ꢀM.ꢀAvlasevich,ꢀY.ꢀS.;ꢀSchoeller,ꢀW.ꢀW.;ꢀUllen,ꢀK.ꢀM;ꢀ
Bardeen,ꢀ C.ꢀ J.ꢀ Excitonꢀ Fissionꢀ andꢀ Fusionꢀ inꢀ Bis(tetracene)ꢀ
Moleculesꢀ withꢀ Differentꢀ Covalentꢀ Linkerꢀ Structures.ꢀ J.ꢀ Am.ꢀ
Chem.ꢀSoc.ꢀ2007,ꢀ129,ꢀ14240–14250.ꢀ(b)ꢀBurdett,ꢀJ.ꢀJ.;ꢀBardeen,ꢀ
C.ꢀ Theꢀ Dynamicsꢀ ofꢀ Singletꢀ Fissionꢀ inꢀ Crystallineꢀ Tetraceneꢀ
andꢀCovalentꢀAnalogs.ꢀJ.ꢀAcc.ꢀChem.ꢀRes.ꢀ2013,ꢀ46,ꢀ1312–1320.ꢀ
(
c)ꢀStern,ꢀH.ꢀL.;ꢀMusser,ꢀA.ꢀJ.;ꢀGelinas,ꢀS.;ꢀParkinson,ꢀP.;ꢀHerz,ꢀL.ꢀ
M.;ꢀBruzek,ꢀM.ꢀJ.;ꢀAnthony,ꢀJ.;ꢀFriend,ꢀR.ꢀH.;ꢀWalker,ꢀB.ꢀJ.ꢀIdenti-
ficationꢀofꢀaꢀTriplet-pairꢀIntermediateꢀinꢀSingletꢀExcitonꢀFis-
sionꢀinꢀSolution.ꢀProc.ꢀNatl.ꢀAcad.ꢀSci.ꢀU.ꢀS.ꢀA.ꢀ2015,ꢀ112,ꢀ7656–
7
661.ꢀ (d)ꢀ Korovina,ꢀ N.ꢀ V.;ꢀ Das,ꢀ S.;ꢀ Nett,ꢀ Z.;ꢀ Feng,ꢀ X.;ꢀ Joy,ꢀ J.;ꢀ
Haiges,ꢀR.;ꢀKrylov,ꢀA.ꢀI.;ꢀBradforth,ꢀS.ꢀE.;ꢀThompson,ꢀM.ꢀSingletꢀ
FissionꢀinꢀaꢀCovalentlyꢀLinkedꢀCofacialꢀAlkynyltetraceneꢀDi-
mer.ꢀJ.ꢀAm.ꢀChem.ꢀSoc.ꢀ2016,ꢀ138,ꢀ617–627.ꢀ(e)ꢀStern,ꢀH.ꢀL.;ꢀ
Cheminal,ꢀ A.;ꢀ Yost,ꢀ S.ꢀ R.;ꢀ Broch,ꢀ K.;ꢀ Bayliss,ꢀ S.ꢀ L.;ꢀ Chen,ꢀ K.;ꢀ
Tabachnyk,ꢀM.;ꢀThorley,ꢀK.;ꢀGreenham,ꢀN.;ꢀHodgkiss,ꢀJ.ꢀM.;ꢀAn-
thony,ꢀJ.;ꢀGordon,ꢀM.ꢀH.;ꢀMusser,ꢀA.ꢀJ.;ꢀRao,ꢀA.;ꢀFriend,ꢀR.ꢀH.ꢀVi-
bronicallyꢀCoherentꢀUltrafastꢀTriplet-pairꢀFormationꢀandꢀSub-
sequentꢀ Thermallyꢀ Activatedꢀ Dissociationꢀ Controlꢀ Efficientꢀ
EndothermicꢀSingletꢀFission.ꢀNat.ꢀChem.ꢀ2017,ꢀ9,ꢀ1205–1212.ꢀ
8) (a)ꢀLiu,ꢀH.;ꢀNichols,ꢀV.ꢀM.ꢀShen,ꢀL.;ꢀJahansouz,ꢀS.;ꢀChen,ꢀY.;ꢀHan-
son,ꢀK.ꢀM.;ꢀC.ꢀBardeen,ꢀJ.;ꢀLi,ꢀX.-Y.ꢀSynthesisꢀandꢀPhotophysicalꢀ
Propertiesꢀofꢀaꢀ‘‘Face-to-face’’ꢀStackedꢀTetraceneꢀDimer.ꢀPhys.ꢀ
Chem.ꢀChem.ꢀPhys.,ꢀ2015,ꢀ17,ꢀ6523–6531.ꢀ(b)ꢀLiu,ꢀH.;ꢀWang,ꢀX.;ꢀ
Pan,ꢀL.;ꢀShen,ꢀLi;ꢀWang,ꢀX.;ꢀChenꢀQ.;ꢀLi,ꢀX.-Y.ꢀSynthesisꢀandꢀPho-
tophysicalꢀ Propertiesꢀ ofꢀ aꢀ Bistetraceneꢀ Compoundꢀ withꢀ
(
ꢀ
ꢀ
ACS Paragon Plus Environment