Bandgap Tuning in Molecular Alloy Crystals Formed by Weak Chalcogen Interactions - Thomas et al. - 2021 - Unknown

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pubs.acs.org/JPCLLetterBandgapTuninginMolecularAlloyCrystalsFormedbyWeakChalcogenInteractionsSajeshP.Thomas,ReshmiThomas,ThomasBjørnE.Grønbech,MartinBondesgaard,ArefH.Mamakhel,VictoriaBirkedal,andBoB.Iversen*CiteThis:J.Phys.Chem.Lett.2021,12,3059−3065ReadOnlineACCESSMetrics&MoreArticleRecommendations*sıSupportingInformationABSTRACT:Wedemonstratesystematictuningintheopticalbandgapsofmolecularcrystalsachievedbythegenerationofmolecularalloys/solidsolutionsofaseriesofdiphenyldichalcogenidescharacterizedbyweakchalcogenbondinginteractionsinvolvingS,Se,andTeatoms.Despitethevarietyinchalcogenbondinginteractionsfoundinthisseriesofdichalcogenidecrystals,theyshowisostructuralinteractiontopologies,enablingtheformationofsolidsolutions.ThealloycrystalsexhibitVegard’slaw-liketrendsofvariationintheirunitcelldimensionsandanonlineartrendforthevariationinopticalbandgapswithrespecttotheircompositions.Energy-dispersiveX-rayandspatiallyresolvedRamanspectroscopicstudiesindicatesignificanthomogeneityinthedomainstructureofthesolidsolutions.Quantumperiodiccalculationsoftheprojecteddensityofstatesprovideinsightsintothebandgaptuningintermsofthemixingofstatesinthealloycrystalphases.ttemptstotunematerialpropertiesviaalloyformationtransferinteractionswherethestoichiometryofthedonororA14,15datebacktothebronzeage.Generatinghigh-entropyacceptormoleculesisvaried,and(III)alloysof1,2metallicalloysorsolidsolutionsofknownstructuraltypesofisostructuralcompoundswithahighdegreeofshapeandinorganiccompoundsisanefficientwaytoalteroptical,16−22sizesimilarity.Recently,Desirajuetal.demonstratedthe3−6electronic,andcatalyticproperties.Theformationofsolidmechanicalhardeningofsolidsolutionsformedbytautomerssolutionsofinorganicmaterialsisquitecommon,asitis23ofthedrugomeprazole.Infunctionalmolecularmaterials,facilitatedbysimilarityinatomic/ionicradii,valency,andalloyscanhavepromisingapplicationsinbandgapengineeringDownloadedviaBUTLERUNIVonMay16,2021at08:50:29(UTC).oxidationstatesoftheatomsorionsthatcanoccupysimilaroforganicsemiconductorsandphotovoltaiccrystals.24crystallographicpositions.However,examplesoforganicsolidCompositionvariationwithrespecttotheionicspeciesin7,8solutionsthatformmolecularcrystalsareratherrare.Theorganic−inorganichybridperovskitestructures,metal−organicfactthatmoleculeshaverathercomplexandirregularshapesframeworks,andsaltshavebeenreportedtoshowtuninginandhighlydirectionalintermolecularinteractionsmakesittheiroptical/electricalproperties.25,26However,studiesthatSeehttps://pubs.acs.org/sharingguidelinesforoptionsonhowtolegitimatelysharepublishedarticles.difficulttosubstituteamoleculeincrystalbyachemicallydemonstratesystematictuningintheopticalbandgapsindifferentmolecule.Crystalengineeringapproachestodesignmolecularsolidsolutionswithdetailedcrystallographicstudiesmulticomponentcocrystalshavebeenshowntobeeffectiveinonthestructure−propertyrelationsareraretoourknowledge.modulatingthechemicalandphysicalpropertiesofmolecularSolidsolutionsoftypeIaredistinctinthesensethattheylacksolidsrelevanttopharmaceuticalchemistryandmaterialdirectinteractionsbetweentheguestmoleculesofwhichthe9science.Whileacocrystalhasadefinitestoichiometryofstoichiometriesaretuned,makingitdifficultfortheelectronicconstituentmolecules,continuouslyvaryingstoichiometriesstatesofthecomponentstomix.FortypeIIcrystals,althougharepossibleforasolidsolution.Beingabletovarythethedirectinteractionbetweenthevaryingmolecularstoichiometryofmolecularcomponentsincrystalsmightcomponentsarelimited,thestrongπ···πstackingcanleadtoprovidemeanstofine-tunetheopticalandelectronicpropertiesofmolecularmaterialswithawiderangeofapplications.MostexamplesoforganicsolidsolutionsareReceived:February25,2021formedbyoneofthefollowingstructuraltypes(seeFigure1):Accepted:March15,2021(I)porousorhost−guestcrystalstructureswithvaryingPublished:March19,2021stoichiometryofmolecules/atomsconstitutingthehost10−13frameworksortheguests,(II)donor−acceptortypemolecularcomplexesformedbystrongπ···πstackingorcharge©2021AmericanChemicalSocietyhttps://doi.org/10.1021/acs.jpclett.1c006143059J.Phys.Chem.Lett.2021,12,3059−3065

1TheJournalofPhysicalChemistryLetterspubs.acs.org/JPCLLettereachother.Thecellparametersincreasegraduallyfromthesulfuranalogue(dpdS)tothetelluriumanalogue(dpdTe).Theirunitcellvolumesareinthefollowingorder:Vcell(dpdS)=1079.8(2)Å3

2TheJournalofPhysicalChemistryLetterspubs.acs.org/JPCLLetterqualitysinglecrystalsobtainedforaseriesofdifferenttuningintheopticalandelectronicpropertiesaswell,similarstoichiometriesfordpdS−dpdSesolidsolutions(dpdSxSe1−x)tothetrendsreportedformanyinorganicsolidsolutionenabledtheaccuratedeterminationoftheirunitcellsemiconductors.ThephysicalevidencefortheopticalbandgapparametersandcompositionsbyusingX-raydatacollectedtuningindpdSxSe1−xanddpdSexTe1−xsolidsolutionwasat280K.Thecompositionsofindividualmolecularimpliedbythecolorchangesinthesecrystals.ThecrystalsofcomponentsweredeterminedbycarefulcrystallographicdpdS,dpdSe,anddpdTearecolorless,yellow,anddarkred,occupancyrefinementsofSversusSeatomsinthesecrystalrespectively.Interestingly,thecrystalsofthemolecularsolidstructures.TwodifferentstrategieswereadoptedforthesolutionsdpdSxSe1−xexhibitedpaleyellowcolor,andthoseofoccupancyrefinement(i)keepingtheatomicdisplacementdpdSexTe1−xshowedorangecolor(Figure3a−c).Thisimpliesparameters(ADPs)ofbothSandSeatomsconstrainedtobesamewhilerefiningtheiroccupanciesand(ii)theADPsofbothSandSeatomswerefixedtothevaluesfromtheparentcrystalstructuresofdpdSanddpdSe(seetheSupportingInformationfortherefinementdetails).Theoccupancyvalues(therebythecomposition)obtainedbyboththesemethodsdifferedbyaround4−8%,andthevaluesfromtherefinementmethod(i)wereusedforfurtheranalysisanddiscussionhere,asitresultedinsignificantlybetteragreementparametersintherefinement(R-factor,residualelectrondensity,etc.)ascomparedtomethod(ii).Also,ouranalysisrevealedthatdifferentsinglecrystalsfromthesamecrystallizationexperi-mentexhibitedvariationsincomposition(upto9%variationfor1:1alloys,andameanabsolutedeviationofaround3%fromthemeancompositionvalues;seeTablesS3andS4).Weobservedasystematicvariationinthecellparametersofthesolidsolutionswithrespecttotheircomposition(Figure2a−d).Figure3.Manifestationofopticalbandgaptuninginmolecularsolidsolutionsascolorchangeincrystalsof(a)dpdSe,(c)dpdTe,and(b)thesolidsolutioncrystalofdpdSexTe1−x.(d,e)NonlineartrendobservedintheopticalbandgapsofmolecularsolidsolutionsofdpdS−SeanddpdSe−Tewiththeircompositions.thatthetuningoftheopticalbandgapsisindeedpossiblebytheformationofsolidsolutions.Itmaybenotedthatsuchagradualvariationincolorwasreportedinaccidentlyformedsolidsolutioncrystalsofcis-mer-MoOCl2(PMe3)3withtheimpuritymer-MoCl3(PMe3)3alongwithanapparentvaria-tioninMo−Obondlengths(asanartifactofcrystallographic47,48disorder).Toquantitativelyexaminethis,weanalyzedthebandgapsoftheparentcrystalsaswellasthesolidsolutionsdpdSxSe1−xanddpdSexTe1−x.TheUV−visreflectancespectraofthegroundsamplesofthecrystalsweretransformedintoTaucplotsbyusingKubelka−Munkfunctionsaspertheestablished49,50method.TheopticalbandgapsoftheparentcrystalsFigure2.SystematicvariationsofunitcellparametersinthesolidsolutionsofdpdSanddpdSeshowingVegard-liketrendswiththeexaminedinthisstudyarethefollowing:Egap(dpdS)=3.47eV,percentagecompositionofdpdSinthesolidsolutions.Egap(dpdSe)=2.76eV,andEgap(dpdTe)=2.34eV.Thebandgapsofthesolidsolutionswerefoundtobesystematicallyvaryingbetweenthevaluesoftheirparentcomponents.Inthecontextofinorganicsolids,suchavariationiswellHowever,thetrendinthisvariationwasfoundtobefarestablishedandisgivenbyVegard’slaw:a(A(1−x)Bx)=(1−x)fromlinearandmimickedanexponentiallikecurveforbotha(A)+xa(B),wherea(A)anda(B)arethelatticeparametersdpdSxSe1−xanddpdSexTe1−xsolidsolutions(Figure3d,e).Itisofthepureparentcrystals,a(A(1−x)Bx)isthatofthesolidnotablethatforthedpdSxSe1−xsolidsolutionsofcompositions45,46solutions,andxisthemolarfractionoftheconstituentB.40%and60%thebandgapvaluesare2.84and2.88eV,However,studiesofsuchtrendsformolecularsolidsolutionsrespectively,whichareclosertothebandgapvalueofdpdSe15,18arerare.RecentworksbyThomasetal.andMatzgeretal.muchlowerthantheaveragebandgapvaluesfortheparentsuggestedthatmolecularsolidsolutionscouldalsoshowcomponents(3.12eV).Asimilartrendwasobservedforthe15,18Vegard’slaw-likecorrelations,albeitwithsomeoutliers.InbandgapsofdpdSexTe1−xsolidsolutionswiththeircomposi-thisstudy,Vegard-likevariationsinthecellparametersoftions.Toourknowledge,suchasystematictrendinbandgapdpdSxSe1−xmolecularsolidsolutions(despitesmalldeviationstuningofmolecularalloyshasnotbeenreported.Ininorganicfromlinearity)pointtothepossibilityofsuchsystematicsolidsolutions,thereareexamplesofbothlinearvariationof3061https://doi.org/10.1021/acs.jpclett.1c00614J.Phys.Chem.Lett.2021,12,3059−3065

3TheJournalofPhysicalChemistryLetterspubs.acs.org/JPCLLetter51,52Egap(suchasZnS(1−x)Sex)andnonlinearvariationssuchas53−55“bowing”(forexample,In(1−x)AlxN).IntheexamplereportedbyPeietal.,thebandgapofthesolidsolutionwasshowntobelowerthanthebandgapvaluesoftheparent27componentsasopposedtoasystematictuning.TheloweredbandgapfoundinthatexamplewasattributedtotheformationofJ-aggregatesbetweenthemolecularcomponentsinthealloymatrix.Inthequaternarycharge-transfersolidsolutionsreportedbyMatzgeretal.,thesmallandirregularchangesobservedintheopticalbandgapsofsolidsolutionswerelinkedtostrongcharge-transferinteractionbetweendonorandacceptormoleculesandthevariationintheextentofcharge15transfer.ItisinterestingtonotethatthealloysinthisstudyexhibitrelativelyweakintermolecularinteractionssuchasC−H···S,C−H···Se,C−H···Te,Se···Se,andTe···πchalcogenbonding.Hence,ourresultsindicatethatbandgaptuningcouldberealizedeveninmolecularcrystalswithsuchweakinteractionsdevoidofanystrongdonor−acceptorcharge-transferinteractionsorπ···πstacking.Toexamineifthebandgaptuninginthealloysleadtotuninginemissionproperties,wemeasuredphotoluminescence(PL)ondpdTe,dpdSe,andtheiralloycrystals.However,nosignificantPLemissioncouldbeobservedinthesolid-statesamples,possiblyduetoquenchingeffects(spectragivenintheSupportingInformation).BecauseX-raycrystalstructuresprovideusonlythespatiallyFigure4.Cartoonrepresentationsof(a)heterogeneousdomainstructurewithseparateddomainsofindividualcomponentsand(b)aaveragedpictureofthetwodifferentcomponentsinacrystal,ithighlyhomogeneousdomainstructure.(c)Electronicbandstructuresisimportanttostudythedetailsofthespatialdistributionofoftheparentcompoundswiththedensityofstatesprojectedtodomainsinsolidsolutioncrystals.Twomajorpossibilitiesofchalcogenatom(S,Se,orTe)states:thetotalDOSareaisshadedinthedistributionofthemolecularcomponentscanbeblue,andthechalcogenatomprojectionoftheDOSiscoloredconsideredasshowninFigure4:(a)aheterogeneousorange.(d)DOSplotsfordpdS0.5Se0.5anddpdSe0.5Te0.5withthedistributionwithmicrometer-sizeddomainsofindividualDOScorrespondingtoheavierchalcogenatominyellowandthesumcomponentsformingthecrystallitesofthesolidsolutionsofstatesfromboththechalcogenatomsinorange.and(b)amorehomogeneousdistributionwherethecomponentsaremixedatnanodimensionsoratthemoleculardispersiveX-rayspectroscopic(EDX)analysisofthelevel.Thedomainstructureofthesolidsolutionsisadistributionofdifferentmolecularcomponentsinsinglesignificantfactorinthecontextoftheirbandgaptuning,crystalsofdpdSxSe1−x.TheEDXspectra(withdistinctenergysinceahighlyhomogeneousmixingwouldhelpeffectivepeaksfortheelementsSandSe)weremappedonthecrystalintermolecularinteractionsbetweendifferentmolecularsurfacewithaspatialresolutionof2nm.Figures5a−cshowcomponentsinthealloyphases.TheobservedtuninginthethattheEDXspectralmapshaveSandSepeaksfromopticalbandgapsmaybeunderstoodintermsofasubmicrometerregionsonthecrystals,indicatinganearlyhomogeneousmixingofdifferentmolecularcomponents,homogeneousdomainstructure.Inaddition,wequantifiedthewhichinturnwouldimplytheoccurrenceofhetero-chalcogenpercentagecompositionofindividualcomponentsbyintegrat-bondssuchasS···SeorSe···Teinteractionsinthesolid−ingtheareaunderthespectralpeakscorrespondingtoSandsolutioncrystals.TheX-raymodelsofdpdSxSe1−xandSeseparately.dpdSexTe1−xshowedS···Sehetero-chalcogenbondingofBecausetheEDXmappinganalysiswasperformedona3.644(1)ÅandSe···TechalcogenbondinginteractionsofsinglecrystalforwhichgoodqualityX-raydiffractiondatawere3.810(1)and4.092(1)Å.Wecalculatedthebandstructuresofalreadycollected,theelementalcompositionfromEDXwasthesesolidsolutionsincomparisonwiththeparentcomparedtothevaluesfromtheSXRDoccupancyrefinementcompoundsusingtheX-raycrystalstructuresasinputsinmodels.ThedpdScompositionof59%(esd∼3.5%)obtainedperiodicquantumchemicalcalculations.TheanalysisofthefromtheEDXmapmatchedwelltheoccupancyvalueof59%projecteddensityofstates(DOS)intoelementalcontributions(e.s.d.∼1%)fromtheSXRDmodelbymethod(i).Thegoodshowedthattheenergystateslyinginthebandedges(highestagreementbetweentheresultsfromSXRD(abulkmeasure-occupiedstatesandlowestunoccupiedstates)arepredom-mentfromthesinglecrystal)andEDX(surfacemapping)inantlyfromthechalcogenatomssuchasS,Se,andTeinfurthervalidatesthehomogeneityofdomaindistributionasdpdS,dpdSe,anddpdTe,respectively(Figure4c).TheDOSwellasourX-rayoccupancymodelingstrategy.Inaddition,toplotsofthesolidsolutionsrevealthatthemixingofstatesprobeanycharacteristicspectroscopicfeaturescorrespondingindeedleadtotheshiftsintheelectronicstatesatthebandtothesolidsolutions,weperformedspatiallyresolvedRamanedgesandtheloweringofthebandgap(seetheSupportingstudiesonthesinglecrystalsofdpdSxSe1−x.ThecharacteristicInformationfordetails).TheseresultsfurtherdemonstratethatpeakscorrespondingtotheS−Sbondvibrations(541cm−1)amixingofthecomponentphasesatamicroscopiclevelisandSe−Sebondvibrations(312cm−1)inthedpdSSex1−xindeedessentialforeffectivebandgaptuning.Hence,tocrystalswerefoundtobeatthesamepositionsasintheirinvestigatethedomainstructure,weperformedenergyparentcrystals(dpdSanddpdSe).However,theratiosofpeak3062https://doi.org/10.1021/acs.jpclett.1c00614J.Phys.Chem.Lett.2021,12,3059−3065

4TheJournalofPhysicalChemistryLetters■pubs.acs.org/JPCLLetterASSOCIATEDCONTENT*sıSupportingInformationTheSupportingInformationisavailablefreeofchargeathttps://pubs.acs.org/doi/10.1021/acs.jpclett.1c00614.CrystallographicdatatablesanddetailsofRaman,EDX,UV−visdiffusereflectancespectroscopicmeasurements,anddetailsofcomputationalcalculations(PDF)■AUTHORINFORMATIONCorrespondingAuthorBoB.Iversen−CenterforMaterialsCrystallography,DepartmentofChemistryandiNano,AarhusUniversity,Aarhus8000,Denmark;orcid.org/0000-0002-4632-1024;Email:bo@chem.au.dkFigure5.Top:(a−c)EDXmapsofthedpdS−SesolidsolutionAuthors(59:41)highlightingregionsofdifferentelementalcontentssulfurSajeshP.Thomas−CenterforMaterialsCrystallography,(red),selenium(green),andoverlappedmapshowingnearlyDepartmentofChemistryandiNano,AarhusUniversity,homogeneousdistributionofdpdSanddpdSeinthealloycrystalAarhus8000,Denmark;orcid.org/0000-0003-3552-(scalebar=1μm).Bottom:Ramanspectralpeakscorrespondingto8625S−SandSe−SecharacteristicvibrationsindpdSanddpdSeinthedpdS−Sesolidsolutioncrystaland(e)spatialmappingofS−S/Se−ReshmiThomas−CenterforMaterialsCrystallography,SeRamanintensityratiocorrespondingtothevariationofDepartmentofChemistryandiNano,AarhusUniversity,compositionwithinasinglecrystal.Aarhus8000,DenmarkThomasBjørnE.Grønbech−CenterforMaterialsCrystallography,DepartmentofChemistryandiNano,AarhusUniversity,Aarhus8000,DenmarkintensitiescorrespondingtoS−SmodeandSe−SemodeinaMartinBondesgaard−CenterforMaterialsCrystallography,seriesofdpdSxSe1−xcrystalswerefoundtobevaryingwithDepartmentofChemistryandiNano,AarhusUniversity,respecttothecompositionx,inasystematicbutnonlinearAarhus8000,Denmarkfashion(seeFigureS11).Inaddition,thiscorrelationinArefH.Mamakhel−CenterforMaterialsCrystallography,Ramanpeakintensityratios(IS−S/ISe−Se)wasutilizedtoprobeDepartmentofChemistryandiNano,AarhusUniversity,thevariationofcompositionwithinasinglecrystal.Forthis,Aarhus8000,DenmarkthespatiallyresolvedRamanspectralmapsweretransformedVictoriaBirkedal−InterdisciplinaryNanoscienceCenterintopeakintensityratiomapsasshowninFigure5e.Thefact(iNano)andDepartmentofChemistry,AarhusUniversity,thatpeakintensityratioIS−S/ISe−SevariesinaverysmallrangeAarhus8000,Denmark;orcid.org/0000-0002-1360-suggestedthatthecompositionwithinasinglecrystalisnearly8870uniformalbeitwithsmalldifferences.Completecontactinformationisavailableat:Insummary,thesolidsolutionsdpdSxSe1−xanddpdSexTe1−xhttps://pubs.acs.org/10.1021/acs.jpclett.1c00614reportedhereestablishthatbandgaptuningispossibleeveninmolecularcrystalswhicharestabilizedbyweakinteractionsFundingsuchasS···SorSe···SechalcogenbondsanddevoidofstrongThisworkwassupportedbytheVillumFoundation.S.P.T.charge-transferinteractionsorπ···πstacking.ThedomainacknowledgesEUfundingforMarieSkłodowska-CuriestructureofthesolidsolutionsintermsofthedistributionofIndividualFellowship(Grant798633).componentsprobedbyEDXmappingsuggestedanearlyhomogeneousdistribution.Electronicbandstructurecalcu-NoteslationsrevealedhowthehomogeneousmixingofmoleculesTheauthorsdeclarenocompetingfinancialinterest.leadtomixingofstates,whichinturnleadstoloweringofthebandgaps.X-rayoccupancyrefinementstrategiesestablishedin■REFERENCESthisstudytoobtainaccuratecompositionsmaybegenerally(1)Bondesgaard,M.;Broge,N.L.N.;Mamakhel,A.;Bremholm,applicabletomodelcrystalstructuresofmolecularsolidM.;Iversen,B.B.GeneralSolvothermalSynthesisMethodforsolutions.Theoriginofthesystematic,nonlinearvariationsinCompleteSolubilityRangeBimetallicandHigh-EntropyAlloytheopticalbandgapswithcompositionsneedtobeinvestigatedNanocatalysts.Adv.Funct.Mater.2019,29,1905933.further.Ourstudysuggeststhatalloyformationmaybeapplied(2)George,E.P.;Raabe,D.;Ritchie,R.O.High-entropyalloys.Nat.toawiderrangeofmolecularcrystals,includingtheorganicRev.Mater.2019,4,515−534.optoelectronicmaterialscomposedofsulfurandselenium(3)West,A.R.SolidStateChemistryandItsApplications;JohnWileycompoundsexhibitingweakchalcogenbondsasacrystal&Sons:2014.(4)Chen,S.;Shang,R.;Wang,B.-W.;Wang,Z.-M.;Gao,S.AnA-engineeringstrategyforbandgaptuning.AlthoughthecrystalsSiteMixed-AmmoniumSolidSolutionPerovskiteSeriesofanalyzedinthisstudyshowednosignificantphotophysical[(NH2NH3)x(CH3NH3)1−x][Mn(HCOO)3](x=1.00−0.67).properties,ourongoingworkonorganiclight-emittingdiodeAngew.Chem.,Int.Ed.2015,54,11093−11096.(OLED)materialsshowsthatthemolecularalloystrategycan(5)Wang,F.;Kusada,K.;Wu,D.;Yamamoto,T.;Toriyama,T.;beeffectivelyemployedtotunefluorescenceemissionMatsumura,S.;Nanba,Y.;Koyama,M.;Kitagawa,H.Solid-Solutionproperties.AlloyNanoparticlesoftheImmiscibleIridium−CopperSystemwitha3063https://doi.org/10.1021/acs.jpclett.1c00614J.Phys.Chem.Lett.2021,12,3059−3065

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