Metallo-porphyrin containing zirconium phosphonate thin films : structure and catalysis

187 Pages·2000·7 MB·English

by  Lee, Christine Marie Nixon,

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METALLO-PORPHYRINCONTAININGZIRCONIUMPHOSPHONATE
THINFILMS: STRUCTUREANDCATALYSIS
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By
CHRISTINEMARIENIXONLEE
ADISSERTATIONPRESENTEDTOTHEGRADUATESCHOOL
OFTHEUNIVERSITYOFFLORIDAINPARTIALFULFILLMENT
OFTHEREQUIREMENTSFORTHEDEGREEOF
DOCTOROFPHILOSOPHY
UNIVERSITYOFFLORIDA
2000
ACKNOWLEDGMENTS
First,Iwouldliketothanksomeoftheteacherswhohavepointedmetoward
chemistryandsupportedmeinthislongeducationaladventure. IthankMr.Roger
CraigfromLexingtonHighSchool,forbeingsoexcitedaboutchemistry,andDr.Jim
McCargar,forbeingatirelessambassadorofgeneralandphysicalchemistry,andfor
encouraging(pushing?)metopursueresearchopportunitiesoutsideofBaldwin-
WallaceCollege. IwouldalsoliketothankDr.GaryKosloski,whocaredaboutmy
musicevenafterIdefectedtotheotherhalfoftheliberalartsandsciences. Andto
Dr.JohnWestandDr.WilliamSamuels,Iextendmanythanksforacceptingmeinto
theirresearchprogramsandgivingmetwouniqueandvaluableperspectiveson
researchoutsideoftheacademicenvirorunent.
ImustthankDr.DanTalhamforhispatience,thelimitsofwhich,Ihave
surelytested. Iwouldalsoliketothankhimforacceptingaphysicalpolymer
chemistryconvertandforteachingmetoappreciatematerialsandsurfacechemistry.
Iwouldalsoliketothankhimforhistimeandeffortinencouragingallofustobe
organizedandeffectivespeakersandwriters. Forthat,Iwillbeeternallygrateful.
Icouldnothavecompletedthisdocumentortheresearchthatitdescribes
withoutthecollaborativeassistancefromtheBujoligroupinNantes,France.
EspeciallytoFabriceOdobel,whohascontributedsignificanttimeandenergyto
u
makingandteachingotherstomaketheporphyrinsandligandsonwhichthis
dissertationisfocused,Merci!
QuicknotesofthanksarealsoduetotheButlerPolymerResearch
LaboratoriesforsharingtheirinstrumentationandtoEricLambersandtheMajor
AnalyticalInstrumentationCenterforallowingmetousetheXPS. Also,thanksto
JoeandRaymondinthechemistrydepartmentmachineshopforworkingwithmeon
designingandbuildingthecatalysisflowcells.
Withoutmanywonderfulfriends,mytimeatUniversityofFloridawouldhave
beenmuchlessenjoyable. So,IthankLouarmTroutman,TraceyHawkins,Deanand
AnnieWelsh,DeniseMain,andDebbyTindall,andofcourse,JenBattenandLeroy
Kloeppner(andAlex)-thegreatestoffriends. IoweJenandLeroyspecialthanks,
notonlyfortheireffortsineditingthisdissertation,butalsofortheirsupportandlove
alongtheway.
Andlastly,myfamily. Allthegratitudeintheworldgoestomymomanddad,
PatandRon,andtomybrothersJoeandJohnandmysoon-to-besister,JuUia.Andto
mygrandmothers,EvelynNixonandMargaretLoeber,andinmemoryofmy
GrandpasBillandLee. Ihavebeentrulyblessed. Thanks,too,tomynewfamily,
GeorgeandAgnes,BrianandGregLeewhoarethebestsecondfamilyIcould
imagine.
Tomyhusband,Larry,mybestfriendandbiggestfan,Iowemorethanksthan
canbeexpressed.
m
TABLEOFCONTENTS
mss.
ACKNOWLEDGMENTS ii
LISTOFTABLES vii
LISTOFFIGURES viii
ABSTRACT xiii
CHAPTERS
1 INTRODUCTION 1
1.1 UltrathinFilms 1
1.1.1 Langmuir-Blodgett FilmsandCharacterization 3
1.1.2 Self-assembledFilms 15
1.2 HybridOrganic/InorganicUltrathinFilmsBasedonLayeredSolids 16
1.2.1 Background 16
1.2.2 Self-assembledFilmsIncorporatingMetalPhosphonate
Binding 19
1.2.3 MetalPhosphonateLangmuir-BlodgettFilms 20
1.2.4 Dual-FunctionLangmuir-BlodgettFilms 23
1.3 BackgroundonPorphyrins 24
1.3.1 OpticalBehaviorofPorphyrins 24
1.3.2 BackgroundonManganesePorphyrins 33
1.3.3 ImmobilizationofPorphyrins 35
1.3.4 HeterocycUcLigandCocatalysts 36
1.4 DissertationOverview 38
2 EXPERIMENTAL 42
2.1 Langmuir-BlodgettandSelf-AssembledFilmPreparationProcedure 42
2.1.1 GeneralLangmuir-BlodgettandSelf-AssemblyProcedures 42
2.1.1 Characterization 46
2.2 PorphyrinFilms 48
2.2.1 PalladiumPorphyrinFilms 48
2.2.2 ManganesePorphyrinFilms 49
IV
2.2.3 ManganesePorphyrin/ImidazoleMixedFilms 51
2.3 Catalysis 53
2.3.1 CatalysisusingPhIOasanoxidant 53
2.3.2 CatalysisusingPeroxidesasoxidants 57
PALLADIUMPORPHYRINCONTAININGZIRCONIUMPHOSPHONATE
THINFILMS 58
3.1 BackgroundonPalladiumPorphyrinFilms 58
3.2 Results 61
3.2.1 UV-visofPalladiumPorphyrinSolutions 61
3.2.2 LangmuirMonolayersofPalldiumPorphyrins 63
3.2.3 Langmuir-BlodgettFilms 69
2.3.3 Conclusions 79
MANGANESEPORPHYRINCONTAININGZIRCONIUM
PHOSPHONATETHINFILMS 83
4.1 Background 83
4.2 UV-visBehaviorofMnTPPs 85
4.2.1 Solutionstudies 85
4.2.2 LangmuirMonolayers 93
4.2.3 Langmuir-BlodgettFilmsofpureMnP4 95
4.2.4 Self-assembledfilmsofMnP4 100
4.3 Conclusions 106
INCORPORATIONOFANIMIDAZOLELIGANDINTOMANGANESE
PORPHYRINCONTAININGZIRCONIUMPHOSPHONATE
THINFILMS 109
5.1 Background 109
5.2 SolutionStudies 113
5.2.1 MnPOandMnP4withImH 113
5.2.2 MnP4andMnPOwithImODPA 115
5.3 FilmStudies 117
5.3.1 Langmuir-BlodgettFilmscontainingsubstitutedMnP4 117
5.3.2 Mn-porphyrinssubstitutedintoself-assembledfilmsof
ImODPA 124
5.3.3 Self-assemblingtheMnP4andImODPAfroma
mixedsolution 130
5.3.4 OthermethodsforpreparingImODPAandMnP4containing
films 131
5.3.5 CharacterizationoffilmscontainingMnP4andImODPA
byXPSandATR-IR 134
5.4 Conclusions 141
6 MANGANESEPORPHYRINANDIMIDAZOLECONTAINING
ZIRCONIUMPHOSPHONATETHINFILMSASCATALYSTS 144
6.1 Background 144
6.2 Results 147
6.2.1 CatalysisWithPhIOastheOxidant 147
6.2.2 CatalysisUsingH2O2astheOxidant 159
6.3 Conclusions 163
REFERENCES 164
BIOGRAPHICALSKETCH 171
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VI
LISTOFTABLES
Table page
3.1 UV-visdatafromsymmetricandalternatingfilmsofPdP4. Xmax.isgivenfor
monolayers,andinterlayerthicknessisgivenformultilayersoffilms
transferredunderavarietyoftransferconditions 71
3.2 UV-visdatafromsymmetricandalternatingfilmsofPdPl. X,maxisgivenfor
monolayers,andinterlayerthicknessisgivenformultilayersoffilms
transferredunderavarietyoftransferconditions 77
6.1 Timedependenceofepoxidationofcycloocteneusing40|amolcyclooctene
and5famolPhIOinImLofsolution. Tothehomogeneousreactionwas
addedInmolofMnPO 151
6.2 Conversionofcyclooctenetocyclocteneoxidewith40|amolcyclooctene
and5i^molPhIOinImLofsolutionusingMnP4LBfilm 154
6.3 Conversionofcyclooctenetocycloocteneoxidewithvaryingcyclooctene
toPhIOratiosinImLofsolutionusingMnP4SAfilmsover24hr 155
6.4 Conversionofcyclooctenetocycloocteneoxidewith40^molcyclooctene
and5^imolPhIOinImLofsolutionandinfilmscontainingimidazole 157
V'e«.
6.5 Comparisonofblanksandhomogeneousepoxidationyieldsinvialsvs.in
thereactioncells 158
6.6 Conversionofcyclooctenetocycloocteneoxidewith400fimolcyclooctene
and80^molH2O2inImLofsolutionusingimidazoleandporphyrin 161
vn
LISTOFFIGURES
Figure page
1.1 Schematicofanisothermandcorrespondingmonolayerbehavior 5
1.2 SchematicofX-,Y-,andZ-typeLangmuir-Blodgettmultilayers 7
1.3 X-raydiffractiondiagram 9
1.4 IllustrationofATR-IRExperiment 10
1.5 SchematicofXPSexperiment H
1.6 SchematicofpolarizedUV-visexperimentalbeamdirections 13
1.7 Behavioroftheobliquedichroicratioversusanorientationparameter(P) 14
1.8 Crystalstructureofzirconiumphosphate 17
1.9 ComparisonbetweentraditionLBfilmsandmetal-phosphonateLBfilms 20
1.10 Schematicofformationofdivalentortrivalentmetalphosphonatefilms 22
1.11 Structuresofporphyrin-typemolecules A)porphineB)freebase
porphyrin,andC)pthalocyanine 25
1.12 UV-visspectrumofametallo-porphyrin(PdTPP) 25
1.13 Outlineof16-memberprincipleresonancestructureofmetallo-porphyrin 26
1.14 Gouterman'sfour-orbitalmodel 27
1.15 Transitiondipolemomentsinmetallo-porphyrin 30
1.16 Porphyrinchromophoreinteractions: Thesquarerepresentsthe
chromophoreanditsdisectingaxes. A)H-typeorface-to-face
aggregates;B)edge-to-edgeaggregates; C)J-typeorhead-to-tail
aggregates 32
1.17 SuggestedmechanismofolefinepoxidationcatalyzedbyMnTPP 35
vui
2.1 SchematicofLangmuir-Blodgetttroughandmonolayer 42
2.2 Schematicofthethree-stepdepositionprocessusedforzirconium
phosphonatefilms 45
2.3 Schematicofcatalysiscell,sideview 54
2.4 Schematicofcatalysiscell,topview 55
3.1 StructuresofA)PdP4andB)PdPl 59
3.2 SchematicofPd-porphyrinfilmsformed: a)alternatingODPA/Zr/PdP,
b)alternatingODPA/Zr/PdP:ODPAmixedfilm,c)symmetric
PdP/Zr/PdP,d)symmetricPdP:ODPA/Zr/PdP:ODPA 60
3.3 SolutionUV-visofPd-porphyrinsinCHCI3:A)PdP4,B)PdPl 62
3.4 SolutionUV-visofPdP4inEtOHandwatercomparedtoCHCI3 63
3.5 IsothermsofPdP4,pureandmixedwithODPA(PdP4:0DPA),ona
watersubphase 64
3.6 ReflectanceUV-visofPdP4onwatersubphase 65
3.7 IsothermsofPdPl,pureandmixedwithODPA(PdPl:ODPA),ona
watersubphase 66
3.8 ReflectanceUV-visofPdPlonwatersubphase 67
3.9 ReflectanceUV-visof10%PdP4:90%ODPAonawatersubphase 68
3.10 Meanmolecularareavs.ratioofODPA/Porphyrin:A)PdP4,B)PdPl 69
3.11 TransmissionUV-visofPdP4filmstransferredathighandlowMMA.
Absorbancescalecorresondstothefilmtransferredat300A^molecule'' 72
3.12 UV-visofSAPdP4filmsrinsedinhotCHCI3 75
3.13 TransmissionUV-visoffilmsofPdPltransferredathighandlowMMA 76
3.14 AbsorbanceofSoretvs.timerinsedinhotCHCI3:A)PdP4,B)PdPl 78
3.15 IllusltorwatMionMoAforientationandpackingofPdP1filmstransferredathighand 79
IX
31
3.16 IllustrationoforientationandpackingofPdP4filmstransferredathighand
lowMMA
80
4.1 StructuresofA)MnP4andB)MnPO 84
4.2 UV-visofMnPOinCHCI3 87
4.3 SolventbehaviorofMnP4inwater,EtOHandCHCI3 88
4.4 UV-visconcentrationstudyofMnP4inCHCI3:a)10"^M,b)10"^M 88
4.5 MnPbdO))31inXXC11H00C""*^I3MM(1eettxhhyylllOpp"'hhooMss)pphhwooinntiihcceaatcciihddy,,lpce))hop2supxrheo1n0M"in^cPMa4ciedt:hya)lpphuorsepMhonnPiOc,acid, 90
4.6 SolutionUV-visinvestigationofMnP4'ssensitivitytodisplacementof
R-PO(OH)^bychlorideat1x10"^M. Thearrowsindicatethechanges
0in.0thMeitnote0n.s1itMyowfhitlheeptheeakcsonacsetnhteracthiloonriodfeMcnonPc4ensttraayticoonnscthaanntgiensCfHrCoIm3 93
4.7 IsothermofMnP4onwatersubphase 94
4.8 ReflectanceUV-visofMnP4onwatersubphase 95
4.9 UV-visofMnP4cappinglayerstransferredontoODPA/Zratdifferent
surfacepressures(indicatedbythearrows) 96
4.10 LBfilmsofMnP4transferredatA)15mN/mandB)5mN/mrinsedin
CHCI3 98
4.1 MnP4transferredbyLBat0.7mNm''andrinsedinCH3CN: A)
transferredfroma0.5mgmL''solution 99
4.12 MnP4transferredfrom0.1M[Cf]aqueoussubphaseat4mNm"' 100
4.1 MnP4self-assembledfromEtOH/H20andrinsedinCHCI3. Thelegend
indicatesthespectraafterrinsing,afterbeingleftovernightandthe
rinsedagainoverathreedayperiod 101
4.14 SAMnP4filmswithrinsinginhotCH3CN 102
4.15 UV-visresponseofaSAMnP4filmduringrinsingwithhotCH3CN 103
4.16 UV-visofMnP4self-assembledfilmsbeforeandafterrinsinginhotEtOH 104
4.17 MnP4self-assembledfroma0.1Mchloridesolution 105