Electronic structure of tetra(4-aminophenyl)porphyrin studied by photoemission, UV–Vis spectroscopy and density functional theory

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DOI: 10.1016/j.elspec.2017.05.005

URL : http://dx.doi.org/10.1016/j.elspec.2017.05.005

To cite this version : Giovanelli, Luca and Lee, H.-L. and Lacaze-Dufaure,

Corinne and Koudia, Mathieu and Clair, Sylvain and Lin, Y.-P. and Ksari,

Younal and Themlin, Jean-Marc and Abel, Mathieu and Cafolla, Attilio A.

Electronic structure of tetra(4-aminophenyl)porphyrin studied by

photoemission, UV–Vis spectroscopy and density functional theory. (2017)

Journal of Electron Spectroscopy and Related Phenomena, vol. 218. pp. 40-45.

ISSN 0368-2048

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Electronic

structure

of

tetra(4-aminophenyl)porphyrin

studied

by

photoemission,

UV–Vis

spectroscopy

and

density

functional

theory

L. Giovanelli

a,b,∗

_,

_H.-L.

_Lee

c,d

_,

_C.

_{Lacaze-Dufaure}

e

_,

_M.

_Koudia

a,b

_,

_S.

_Clair

a,b

_,

_Y.-P.

_Lin

a,b

_,

Y. Ksari

a,b

_,

_J.-M.

_Themlin

a,b

_,

_M.

_Abel

a,b

_,

_A.A.

_Cafolla

c

a_Université_{d’Aix-Marseille,}_IM2NP,_Avenue_Escadrille_{Normandie-Niemen,}_F-13397_Marseille_Cedex_20,_France b_CNRS,_IM2NP_(UMR_7334),_{Marseille-Toulon,}_France

c_School_of_Physical_Sciences,_Dublin_City_University,_Dublin_9,_Ireland d_School_of_Chemical_Sciences,_Universiti_Sains_Malaysia,_Penang,_Malaysia

e_CIRIMAT,_Université_de_Toulouse,_CNRS,_INPT,₄_allée_Emile_Monso_BP44362,₃₁₀₃₀_Toulouse_Cedex_4,_France

Keywords:

Substitutedtetra-phenylporphyrins Photoemission

DFT

UV-Visspectroscopy

a

b

s

t

r

a

c

t

Thevalenceandconductionbandsofathinfilmoftetra(4-aminophenyl)porphyrin(TAPP)are investi-gatedbydirectandinversephotoemissionaswellasbycomparisontodensityfunctionaltheory(DFT) calculations.Byprojectingtheelectroniceigenfunctionsontothemolecularframeworkitwaspossible tointerprettheoriginofeachspectroscopicfeature.Althoughthemajorityofthephotoemission spec-trumisattributedtotheunsubstitutedtetraphenylporphyrin(TPP)parentmolecule,severalfeatures areclearlyduetotheaminosubstitution.Substitutionalsohasimportantconsequencesfortheenergy positionsofthefrontierorbitalsandthereforeonthelow-energyelectronicexcitations.Themeasured electronictransportenergygap(Eg=1.85eV)betweenthehighestoccupiedmolecularorbital(HOMO)

andlowestunoccupied(LUMO)inTAPPisfoundtobesignificantlyreducedwithrespecttoTPP. More-over,anincreasedenergyseparationbetweenthetwohighestoccupiedstates(HOMOandHOMO−1)is foundbothexperimentallyandbyDFTcalculations.SuchevidenceisattributedtoanincreasedHOMO orbitaldestabilizationduetoanenhancedelectron-donorcharacterofthephenylsubstituentsupon aminofunctionalization.Finally,theabovefindingstogetherwithfurthertime-dependentDFT calcula-tionsareusedtointerprettheeffectoftheaminogroupsontheUV–Visabsorptionspectrum,namelyan overallred-shiftofthespectrumandremarkableintensitychangeswithintheQband.

1. Introduction

Porphyrinsareawidelystudiedclassofchromophoresplaying acrucialroleinseveralbiologicalphenomena.The-conjugated electronsystemofthecentralmacrocycleisattheoriginofmany ofthephoto-chemicalpropertiesofporphyrinssuchaslight har-vesting[1,2],cancerphoto-dynamictherapy[3],molecularoxygen transport[4],etc.Engineeringoftheopto-electronicpropertiesof porphyrinsthuscontinuestostimulateanintenseresearchactivity. Importantmodificationtotheporphyrinspectralresponsecanbe obtainedforinstancebyfunctionalization[5,6],nano-structuration ofextendedporphyrin-basedarchitectures[7,8]oradsorptionon asubstrate[9–11].

∗ Correspondingauthorat:Universitéd’Aix-Marseille,IM2NP,AvenueEscadrille Normandie-Niemen,F-13397MarseilleCedex20,France.

E-mailaddress:[email protected](L.Giovanelli).

Theopticalspectraofporphyrinsandporphyrin-based mate-rialsdependcruciallyontheirfrontiermolecularorbitals (MOs) [12–14]. This is well known since the cyclic polyene [15] and Goutermanfour-orbital[12,13]modelswhich havebeen subse-quentlysupportedbyseveralabinitiostudies(seeforinstance[16] andreferences therein).Thepossibilityof modifyingtheenergy ofsuch orbitals bysubstitutionof theporphyrinring has stim-ulateda greatdeal ofworkinrecent years.For instance,ithas beenshownthataddingfunctionalgroupstotheporphin macro-cycleatthemethinebridgeslinkingtogetherthefourpyrrolerings (that is meso-substitution) produces an overall red shiftof the opticalabsorption spectrumassociated witha reduction ofthe HOMO–LUMO gap[17]. Moreover,substitution causes a hyper-conjugativedelocalization of porphyrin states that splitsthe quasi-degeneracyoftheHOMOorbitals[18].Eventuallythishas importantconsequencesonthewavelengthandintensityoftheB (Soret)andQbands,e.g.theQbandscanbeenhancedbylifting thedegeneracyoftheHOMOorbitals[14]).Tetra-phenyl

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substitu-tionisintenselystudiedinthisregardasitiscommonlyperformed andhasastronginfluenceontheopticalspectra[17,19].Several theoretical and experimentalstudieswere performedon tetra-phenylporphyrin(TPP)leadingtoaconsistentunderstandingof therelated opto-electronicstructure [12,17,16,19,20].A natural developmentconsistsofsubstitutingtheTPPphenylswith func-tional groups capable of tuning the opto-electronic properties [21,22].Veryrecentlyperipheralfunctionalizationwasalso stud-iedtodevelopnano-structurationproperties[23–25]includingthe formationofcovalentorganicnetworks[26–28].

BystudyingindetailthefilledandemptyMOsaswellasthe opti-callyexcitedstatesoftetra(4-aminophenyl)porphyrin(TAPP),the presentpaperaimstooutlinethemodificationsinducedbyadding electron-donoraminogroupsatthebenzenepara-positionofTPP. Bypayingspecialattentiontothemodificationoftheelectronic transportgap(Eg)andthebindingenergy(BE)ofthefourfrontier

MOs,itisshownthatphotoemissioncombinedwith(density func-tionaltheory)DFTcalculationscanbeapowerfultooltopredictthe opticalpropertiesofindividualmolecules.

Thefirstpartofthepaperreportsondirectandinverse photoe-missiontakenonthinfilmsofTAPP.Bycomparingthespectrato previousstudiesitwasfoundthat:(i)theelectronictransportgapis 1.85eV,smallerthanthatforTPP[29];(ii)severalspectroscopic fea-turesnotpresentintheTPPspectrumaredetectedintheoccupied stateswhereastheunoccupiedstatesarealmostunchanged. Den-sityfunctionaltheory(DFT)calculationsusingtheB3LYPexchange correlationfunctionalwereperformedonbothTAPPandTPP.The comparisonshowsthatthespectraldifferencesoriginatefromMO havingimportantcontributionfromtheaminogroups and sub-stitutedphenyls.Moreover,aclearchangeuponsubstitutionwas foundintheenergyseparationofthelow-lyingmacrocycle-related HOMOandHOMO−1.Suchevidenceiscorroboratedbythepresent photoemissiondata.Finallytheevolutionfoundintheelectronic structure upon substitution is used tointerpret thechanges in theUV–VisspectrumofTAPPinsolutionthroughthefour-orbital model.Theinterpretationissupportedbytime-dependentTD-DFT calculationsofthelow-energysingletexcitedstates.

2. Experimentalandcomputationaldetails 2.1. Experiment

Valence band ultra-violet photoelectron spectroscopy (UPS) and conductionbandinversephotoelectronspectroscopy (IPES) experiments were performed in two different ultra-high vac-uum (UHV)experimentalapparatus.For UPS thesubstrate was the Au(111) surface, prepared by repeated cycles of standard sputtering(Ar+ _of_0.8_keV_kinetic_energy)_and _annealing₍₇₂₅_K).

Commercially available TAPP molecules (5,10,15,20-tetrakis(4-aminophenyl))porphyrin(CAS22112-84-1,TokyoChemical Indus-try) were first vacuum-sublimated on a glass tube to improve purity. Theresulting deposit wasscraped off and subsequently sublimatedinUHVfromaMocrucibleheatedatabout675Kby aWfilament.Thedepositionratewasabout1MLperhour. Pho-toelectronspectroscopymeasurementswereperformedatroom temperaturebyanOmicron125EAanalyzerwithstandardMg,K˛

andUVHeIsources.X-rayphotoelectronspectroscopy(XPS)was usedinlowresolutionforcheckingmolecularstoichiometryand forthicknesscalibration.UPSwasperformedwith5eVpassenergy andnarrowanalyzerslitsresultingin100meVenergyresolution. UPSspectraweretakenat45◦ _emission_angle._The_energy_scale

wasreferencedtotheFermilevelofthemetalsampleholder.The samplevacuumlevelwasdeducedfromthesecondaryemission lowenergycutoffafterpolarizingnegativelythesample.Forthe inversephotoemissionexperimenttheTAPPmoleculeswereUHV

sublimatedfromanaluminacrucible.Thesubstratewasa double-layergraphenegrownbythermalannealingofa3×3reconstructed SiC(0001)surface.Duringevaporationthesamplesurfacewaskept very close(fewcm)tothemolecular evaporatorallowingfor a lowerevaporationtemperature(about520K)andhigher deposi-tionrate(about1ML/min). NormalincidenceIPES spectrawere performedin theso-calledisochromatmode, that isby detect-ingphotonsoffixedenergy(9.7eVinthepresentcase)through aband-passdetectorwhilescanningtheincidentelectronkinetic energy[30,31].Theprocesscanbeschematizedasfollows:when theimpingingelectronenterthesamplebycouplingwitha sur-faceorbulkstate,itcandroptoa lowerunoccupiedstatewith theemissionofaphoton.Higherphotoncountsareobtainedfor higher densityof final statesand theempty statesspectrum is thusobtainedbyscanningtheincidentelectronenergy.Alow elec-tronflux(electronguncurrentofabout1mA)wasemployedsoto minimizesampledamage.TheFermilevelwasmeasuredonthe sampleholder whilethevacuumlevel wasinferred froma tar-getcurrentspectroscopymeasurementafterhavingpolarizedthe samplenegatively.TheUV–Visabsorptionspectrumwasrecorded fromasolutionofTAPPindichloromethanebyaUV-2600Shidmazu spectrometer.

2.2. Computationaldetails

AllTAPPstructureswerefullyoptimizedusingconjugate gra-dientmethodswiththeGAUSSIAN03[32]softwarepackage.The B3LYPhybridfunctional[33,34]wasused.Thegeometry optimiza-tionsweredonewiththeB3LYP/6-31G*schemeandthestationary pointswerecharacterizedasminimabyavibrationalanalysis.The energywascalculatedusingthe6-311+G*basisset(singlepoint calculation). Theoptimizationstep wasfollowed bya Mulliken populationanalysisinordertoobtainthechargeandspin den-sityoneachatom.Intheoptimizedgeometry,theamino-phenyl groupsaretiltedby63◦_with_respect_to_the_macrocycle_plane,_in_fair

agreementwithwhatfoundpreviouslyfortheTPPmolecule(67◦₎

[35].Subsequently thegroundstategeometrieswereemployed intheexcitedstatecalculationsusingthespinunrestricted time-dependentDFTmethod[36–38].Theexcitationenergies,calculated usingtheB3LYPfunctionalandthe6-311+G*basisset,thus corre-spondtoverticaltransitions.

3. Resultsanddiscussion

UPSand IPESarepreferredtoolstomonitortheevolutionof thefrontier orbitals of-conjugatedorganicmolecules [39]. In fact,severalstudieshaveproventhatthespectralfeatures mea-suredonthinfilms1 _are_equivalent_to_those_measured_on_better

resolvedgasphase spectra[18,20,40–42] andcanthenbe com-paredtocalculateddensityofstates(DOS).InFig.1theUPSandIPES spectraofathickfilmofTAPPdeposited,respectively,onAu(111) andgraphenearecomparedwiththeB3LYP/6-311+G*DOS calcu-lationsofTAPPandTPPobtainedbyGaussianconvolution(0.2eV FWHM)oftheKohn–Sham(KS)eigenvaluesofthegroundstate configuration(verticalbarsatthebottom).Thefilmthicknessis approximately5ML,thickenoughtoruleoutanyinteractionof theprobedmoleculeswiththesubstrate.Thisissupportedbythe absenceofanysubstratefeaturesuchasAu5dstatesintheUPS[43] orthestrong*featureofgrapheneintheIPES[31].Thebottom energyscalerepresentstheBEoftheUPS/IPESspectrareferenced tothesampleFermilevel,thetopenergyscalereferstothevacuum level.Thesamevalueofthevacuumlevel(Evac=4.3eV)wasfound

1_Organic_molecules_in_thin_films_are_known_to_interact_among_each_other_through

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Fig.1.TAPPUPSandIPESspectra(uppercurves)comparedwithKSeigenvalues(filledandemptystates)ofTAPP(red)andTPP(blue).Thecalculatedspectraareobtainedby convolutionoftheeigenenergies(verticalbars)withaGaussianfunctionof0.2eVand0.5eVFWHMforthefilledandemptystates,respectively.Thecalculatedspectraare shiftedinenergytoalignthephenyl-derivedpeaktotheexperimentalfeatureatabout3.9eV.TheTAPPeigenvalueshavingsubstantialcontributionfromtheaminogroups aredisplayedasgreenbars.ThecalculatedspectralfeaturesofTAPPthatmarkacleardeparturefromtheTPPspectrumarelabeledwithanasterisk.(Forinterpretationof thereferencestocolorinthisfigurelegend,thereaderisreferredtothewebversionofthearticle.)

forthethickfilmofTAPP/Au(111)andTAPP/graphene,allowing theplottingoftheUPSandIPESspectraoftheTAPPonacommon energyscale.BoththeTAPPandTPPcalculatedoccupied eigenen-ergiesandspectrawereshiftedsoastoaligntheBEofthepeakat 3.9eVtoitsexperimentalcounterpart(dashedline).2_A_similar

pro-cedurewasappliedtotheunoccupiedstateswherethecalculated valuesofTAPPareshiftedsotoaligntheLUMOtothe experimen-talvalue.Thesameshiftwasappliedtothecalculatedunoccupied statesofTPP.3

Let us first compare the TAPP experimental and simulated spectra. A first inspection reveals that all the main spectro-scopic features are remarkably well reproduced in energy and intensity.ThisconfirmsthecapabilityoftheB3LYPhybrid func-tionalintreatingsatisfactorilyelectroniccorrelationsofextended -conjugatedorganicmolecules due to thepresence of a frac-tionalexactexchangecoupledwitha non-localpotentialwhich reducestheself-interactionerrorsofsemi-localapproaches(see forinstanceKroniketal.in[44]).Eachoftheeigenstatesreported inFig.1isaMOdelocalizedacrossthemolecule.Amongthese,the HOMOandHOMO−1statesappearasisolatednon-degenerateMO featuresatlowBE.TheyareshowninFig.2(aswellasthoseofthe nearly-degenerateLUMOandLUMO+1) andaresimilartothose foundpreviouslyforthesamesystem[22]andfortheparentTPP molecule[16,17,19,20,45–47].Fortherestofthespectrumeach spectroscopicfeature(peak)resultsfromseveralMOsandthere isnosimpletrendtoattributeitsorigintospecificatomsinthe

2_Such_procedure,_also_used_in_other_studies_[42]_is_necessary_since_the_UPS

spec-trumwastakenonasolidsurface,afactthatisnottakenintoaccountinthe calculations.Thechoiceofthepeakat3.9eVwasmadebecausethispeakisverywell definedanditispresentinun-substitutedTPPallowingthebestoverallagreement betweenexperimentandcalculation.

3_Such_rude_{approximation}_does_not_affect_the_discussion_on_the_amino

contri-butiononthespectralshape.Themodificationoftheenergygapuponsubstitution ismadeonlythroughcomparisonofexperimentaldataofthepresentpaperwith existingliterature.

Fig.2.ThespatialdistributionofthefourTAPP’sfrontierMOs.Althoughthepresent calculationsweremadewithoutsymmetryrestrictionstheresultingMOsarevery similartothoseoftheunsubstitutedfree-baseporphine(seetext).Inordertoease thediscussionthesymmetrylabelsoftheD2hsymmetryarethenreportedinquotes.

molecule.Inthefollowinganassignmentismadebyprojectingthe eigenfunctionscorrespondingtoagivenpeakontothemolecular framework.Thefeaturesofthecalculatedspectrumarenumbered tofacilitatethediscussionandtrendsaregivenontheeffectof theaminogroupsontheDOS.Atbindingenergieshigherthanthe HOMO−1,thereisapeakataround2–3eVwhichisnotfoundinthe UPSspectrumofTPP[18,20,42].Accordingly,thecalculated

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coun-Fig.3. SquaredsumsofseveralMOgivingrisetowell-definedspectroscopic fea-turesintheUPSspectrum.LabelsrefertopeaksinFig.1.Peaks3–10clearlyoriginate fromstateslocalizedonaminogroups.

terpart,Peak3,isabsentinthecalculatedspectrumofTPP(blue curveinFig.1).Theotherfeaturesthatdisplayacleardeparture fromtheTPPexperimental[18,20,42]andcalculatedspectraare Peak6andPeak10.Thesethreepeaksaremarkedwithanasterisk inFig.1.Todeterminethecontributionoftheaminosubstituent tothesefeatures,theeigenenergieshavingsignificantcontribution fromthesegroupsarereportedingreenasaseparatesetof ver-ticalbarsoverthecompletesetofKSeigenvalues.Ascanbeseen thethreefeaturesmentionedabovealloriginatefromtheamino groups.ThiscanalsobeappreciatedinFig.3wheretheMO con-tributingtoPeaks3,6, 9and10 aresummed.Asexpected,the deeperlyingorbitals(namelythosecontributingtoPeaks9and10) showahigher-character(higherinter-atomicorbitaldensity). Fortherestofthespectrumaveryclosesimilarityisfoundwith previousdataonTPPthinfilms[20]andgasphasesexperiments [18,41,42].Specifically,Peak5hasastrongcontributionfromthe fourphenylgroups(butnottheaminogroups)althoughinthecase ofTAPPanimportantspectralweighttoPeak5isalsofoundto comefromthemacrocycle.Feature7hascontributionsfromthe entiremolecule.AthigherBE,theaminosubstituentmodifies siz-ablythefeaturearound8–9eV:thetwopeaksobservedforTPP inthisenergyrange[42]mergeintoasinglefeature.The corre-spondingpeakofthecalculatedspectrum(Peak9)hasasimilar compositiontothatofPeak5exceptthattheaminogroupsalso haveasignificantweight(seealsoFig.3),particularlyatthecenter ofthefeature.

TheunoccupiedpartoftheDOSwasmeasuredbyIPES(right handsideofFig.1).Twointensefeaturesarevisibleinthe spec-trum.Thefirstcomprisesthenearly-degenerateLUMOscentered at1.9eVabovetheFermilevel.Thesecondfeatureiswellseparated fromtheLUMOsandresultsfromthecontributionfromseveral MOs.ForcomparisonthecalculatedunoccupiedstatesoftheTPP arealsoreported.4_As_seen_in_Fig.₁_the_overall_shape_of_the_empty

statesisnotmuchaffectedbyaminosubstitution.

4_The_same_binding_energy_shift_as_that_used_for_TAPP_was_applied_to_the_empty

statesofTPP.

Table1

HOMOtoLUMOEgmeasuredbydirectandinversephotoemissionaswellasHOMO

toHOMO−1energygapvaluesfromUPSandDFT.AllvaluesareineV.

Eg HOMO–HOMO−1

UPS B3LYP

(2B1u–2Au) (b1u–au)

TAPP 1.85 0.40 0.46

TPP 2.5[54] 0.27[18] 0.30

AlthoughnotrigorouslyappropriateforTPPandTAPP,themolecularsymmetryof theMOandexcitedstatesrefers,forsimplicity,toD2hfree-baseporphine.

Table2

TD-DFT-calculatedlowestsinglets(ineV)forTAPPandTPP(takenfrom[19]).Values inparenthesisarethecalculatedoscillatorstrengths(normalizedtotheBband).The fourthcolumnquotestheenergydifferencebetweenthecalculatedBandQband (seetextfordetails).

B Qy Qx B–Q

TAPP 2.97(1) 2.17(0.11) 2.05(0.06) 0.86 TPP 3.19(1) 2.3(0.09) 2.15(0.01) 0.96

Measuringboththefilledandemptystatesofasystemgives access toits electronic transport energy gap (Eg) [48–50].This

isgiven bytheenergy separationbetweentheleadingedgesat theHOMOandLUMOintersectingthezero-emissionbaseline(see Fig.1).InthepresentcaseabandgapEg=1.85±0.10eVisfound

forTAPP, avaluethatis substantiallysmallerthanthevalueof Eg=2.5eVextrapolatedforTPPfromRef.[29].

TheanalysisnowfocussesontheHOMOtoHOMO−1energy separationintheUPSspectrum.ComparingtheavailableUPSdata takenonTPP[18,20,42,51]withthepresentspectrumshowsthat aclearchangeisinducedbyaminosubstitution.Assummarizedin Table1,forTPPingas-phasetheHOMOtoHOMO−1energy sep-arationisreportedtobe0.27eV[18].ForTAPPaleastsquaresfit (notshown)ofthelowenergyregionoftheUPSspectrumwas per-formedusingGaussianfunctions,givingavalueof0.40±0.01eV fortheHOMOtoHOMO−1splitting.5_This_trend_is_also_present_in

thecalculatedspectra(Fig.1 andlastcolumnofTable1)andit isinterestingtorationalizesuchBEchangesuponsubstitution.In free-baseporphine(H2P)thetwoHOMOsarenearlydegenerate

andareassignedasb1uandau(D2hsymmetry).IntheUPSspectra

ofH2Ptheycorrespondto2B1u(HOMO)and2Au(HOMO−1)excited

states, respectively [52], havingan energy separation of 0.2eV [53].Usinggas-phasePESandemployingcross-sectionarguments Gruhnetal.[18]showedthatsubstitutingporphinewithdonor groupsdestabilizestheMOhavingalargerelectrondensityonthe substitutionsite.Forinstance,infree-baseoctaethyl-porphyrine (H2OEP),anchoringoctaethylgroupsatthepyrrolesub-units

desta-bilizestheau MO(noticethefinite contributionfor thisMOat

suchsitesinFig.2).Consequently,theAustateionizationpotential

becomessmallerthanthatoftheB1ustate.TheHOMOpeakisthen

theAustateat0.25eVfromtheHOMO−1B1upeak[18].ForH2TPP

theorderisinverted:thephenylsaresubstitutedinmeso-position atthemethinebridgeswheretheauMOhasanodalplaneandthe

b1uMOhasstrongelectrondensity(seeFig.2).Thelatteris

desta-bilizedbythecharge-donatingphenylsandisthentheHOMOas inH2P.IntheUPSspectrumthecorrespondingB1upeakisfound

at0.27eV(seeTable1)fromtheHOMO−1Aupeak.Inthepresent

caseofTAPP,sincetheaniline(theamino-terminatedphenyl)is knowntobeanelectron-donatingfunctionalgroup,thelarger sep-arationbetweentheB1uandAustatesobservedbyUPSandDFT

indicatesafurtherdestabilizationoftheb1uMO(seeTable1).

5_The_uncertainty_is_mainly_due_to_the_background_used_to_account_for_the

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Fig.4.UV–VisspectraofTAPP(redcurve)andTPP(bluecurvetakenfrom[55])both inadichloromethanesolution.TheintensitywasnormalizedtotheBmaxima.The Q-bandregionsaremultipliedbyafactor10forbettercomparison.Themeasured B−QseparationsaretobecomparedwiththecalculatedvaluesinTable2.(For interpretationofthereferencestocolorinthisfigurelegend,thereaderisreferred tothewebversionofthearticle.)

AredistributionofthefrontierMOisknowntohaveimportant consequencesfortheopticalpropertiesofsubstitutedporphyrins [13,17,46,47,56].InthefollowingtheevolutionoftheUV–Vis spec-traofTPPuponaminosubstitutionwillbeanalyzedinthelight oftheUPS/IPESresultsandcomparedwithTD-DFTcalculationsof thefirstsingletexcitations(Table2).TheUV–VisspectraofTAPP andTPP[55]areshowninFig.4.Bothspectrashowthetypical spectrumoffree-baseporphyrin,namelyanintenseandnarrowB (Soret)bandseparatedinenergyfromthemulti-peakstructureof themuchweakerQband.Beforeanalyzingthedifferencesinduced bytheaminosubstitution,itis usefultorecalltheoriginofthe differentfeaturesobservedinthesespectra.

Withinthefour-orbitalmodel,theenergyseparationand rela-tiveintensityoftheQandBbandsareexplainedintermsofmixing ofexcited-states[12,13].Therelevant opticaltransitionsin this energyrangearebetweenthetwohighestlyingMO(HOMOand HOMO−1)andthetwodegenerateLUMOs.WhentheHOMOand HOMO−1arecloseinenergytheexcitedstatesinteractthrough configurationinteractionthussplittingtheabsorptionspectrum intwo distinct bands(i.e.theBand theQ bands).Remarkably, withinthispicturetheenergysplittingbetweentheBandQbands increases for decreasing HOMO to HOMO−1 energy separation [12,13].Thestrikingintensitydifferencebetweenthetwobands is explained by symmetry arguments. The B band comesfrom symmetry-allowedhigh-energytransitionsinwhichtherelative phaseofthemixingcoefficientsleadstotheadditionofparallel dipolemoments.Themixingforthestabilized,low-lyingexcited statesgivestransitiondipolesofoppositedirectionsresultingin theweakQband[14].InterestinglytheHOMOtoHOMO−1energy splittingalsoaffectstheabsorptionintensity:thecloserthesestates areintheinitialstatethehighertheBtoQintensityratio[12,13].At variancewithmetal-porphyrins,infree-baseporphyrinsthe sym-metryreductioncausestheQbandtosplitintwosetsofpeaks:Qx

andQyhavingdipoletransitionmomentsalignedalongtheN H

bonds(H Haxis)andperpendiculartothemrespectively. More-overeach(0–0)transitionisfollowedbya(1–0)vibronicreplica duetocouplingtoseveralmolecularmodes,themostimportant beingthestretchingmodesatmethinebridges[57–59].

ReturningtoFig.4themoststrikingeffectisthered-shiftof allfeaturesintheTAPPspectrum.UV–Visspectraprobeoptical transitions withinN-electron states whereasMOs measuredby UPS/IPEScorrespondtoN−1andN+1electronstateswhich suf-ferofstrongpolarizationeffectsinthesolidstate.Thisrendersa

directcomparisonbetweenthevaluesoftheUV–VisSoretband andEgmeasuredbyphotoemissioninappropriate.Nevertheless,

thered-shiftintheabsorptionspectrumissuccessfullyreproduced byTD-DFT(Table2)andisinagreementtothereducedelectron energygapmeasuredbyUPS/IPES.Thered-shiftupon donor-meso-substitutionwasthesubjectofintenseresearchinrecentyears. Studieshavepointed outthata sizablein-planenuclear reorga-nizationismostlikelytheoriginoftheobservedeffect[17].This hypothesisseemstoholdinthepresentcasewherethepresence oftheamino groupsisexpected toincrease theelectron-donor characterofthephenyls.

FromafineranalysisoftheUV–Visspectratwoothermajor dif-ferencescanbeobserved.Namely,it isobservedthati) thereis asignificantchangeofintensitieswithintheQ-band:theQx,y(1–0)

peaksarealmostunchangedwhiletheQx,y(0–0)havedoubledtheir

intensity;(ii)thereisareductionoftheQ−Benergyseparation. ThisisevaluatedasthedistancebetweentheBband(considered asasinglefeature)andthehalf-waypointbetweentheQx(0–0)

andQy(0–0)bands[12].Thisvalueis0.97eVfor TPPcompared

to0.86eVforTAPP.Bothaspectsareremarkablywellreproduced byTD-DFTcalculations(Table2)andcanbeunderstoodonthe basis ofthefour-orbitalmodel sketchedaboveand thepresent UPS/IPES/DFTanalysisofTAPP.Infact,photoemissionandDFThave revealed(Fig.1)thataminosubstitutioncausesanincreaseofthe HOMOtoHOMO−1energyseparationtogetherwithanunchanged (withinthepresentenergyresolution)LUMOdegeneracyleading totheenhancementoftheQbandwithrespecttotheBbandaswell asareductionoftheenergyseparationbetweenthetwobands.The factthattheQxy(1–0)replicaremainpracticallyunchangedisnot

surprisingsincesuchreplicaareknownto“borrow”intensityfrom theB-band[57,60]andtheirintensityvarylittleuponsubstitution [60].

4. Conclusions

TheelectronicpropertiesofTAPPwerestudiedbyvalenceband UPS, conduction band IPES and DFT calculations. The compari-sonbetweencalculationsandexperimentisverysatisfactory.The assignmentof the photoemissionspectroscopic features to dif-ferent parts of themolecules was performedand compared to theoreticalspectrumofTPP.Electron-donoramino functionaliza-tionwasfoundtoreducetheHOMO–LUMOelectronictransport gapandtoincreasetheHOMOtoHOMO−1energyseparationina waythatisconsistentwithanorbitaldestabilizationprocess.These findings togetherwithTD-DFT calculations wereused tostudy thechangesuponaminosubstitutionoftheUV–Visspectrum.The presentresultsstronglysuggestthatphotoemissioncanbecome a complementarytool toaddressthemolecular optical proper-ties. Finally,becausethebindingenergy ofthefrontier orbitals isknowntochangewithmolecularconformation[25],combining UPSandDFTwillserveinthefuture–togetherwithSTMandX-ray absorptionspectroscopy–totrackconformationalchangesdue,for instance,tomolecule-substrateinteraction.

Acknowledgements

The Ulysses PHC exchange program as well as the French EmbassyinMalaysiaisacknowledgedforfinancialsupport.AAC acknowledgesfundingfromScienceFoundation Irelandthrough PrincipalInvestigatorgrantSFIP.I.09/IN.1/I2635.

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