ORGANIC/INORGANICLANGMUIR-BLODGETTFILMS BASEDONMETALPHOSPHONATES By MELISSAANNPETRUSKA ADISSERTATIONPRESENTEDTOTHEGRADUATESCHOOL OFTHEUNIVERSITYOFFLORIDAINPARTIALFULFILLMENT OFTHEREQUIREMENTSFORTHEDEGREEOF DOCTOROFPHILOSOPHY UNIVERSITYOFFLORIDA 2000 , Forallthosewhohavegonebeforeme, makingthisjourneypossible... ACKNOWLEDGMENTS Iwasfortunatetohavehadanextremelywonderfulundergraduateresearchexperience, andtheyearsIworkedatMellonInstituteweretrulyspecial. Iamforeverindebtedtomy undergraduateresearchadvisorProfessorRichardD.McCulloughforinspiringinmeapassion forresearchchemistrythatIshallcontinuetoembracewhereverlifemaytakeme. Ihavefond memoriesoftheyearsIspentworkinginhislab,ashisenthusiasmandzealforresearchandall ofitschallengesweresimplycontagious. DuringmystintatCarnegieMellonUniversity,Ihad thepleasureofworkingwithJohnBelot,whotookthetimetoteachanundergraduatewhoknew nothingofbenchchemistryeverythingsheknowsaboutorganicsynthesisandresearch. Icould nothaveaskedforabetterormoreanimatedinstructorandfriend. PaulEwbankhasbeenatruly wonderfulfriendandconversationalistthroughouttheyears,andifhewasnotsupplyingmewith candyandchocolate,hewaseditingmygraduateschoolessaysandinstructingmeonthefiner pointsoflabsafety. IcertainlydomissthoseIceCubes. WhileProfessorMcCulloughwasinstrumentalinkindlingmyfervorforresearch,my graduateschooladvisor,ProfessorDanielR.Talham,wasresponsibleforhoningmyresearch skills. Iamgratefultohimforalloftheemphasisplaceduponimprovingmywrittenandspoken communicationskills. Becauseofhistremendousefforts,IamcertainIhavebecomeamuch betterchemistoverthelastfiveyears. IwishtothankeveryoneintheTalhamresearchgroupfor alloftheirhelpandsupportoverthecourseofmystay. SpecialthanksgotoScottformakingmy transitiontograduateschoolmuchsmootherandforbeingagreatfriendtomeovertheyearsand toJeffforourwonderfulconversationsandforourcountlesssoul-searchingtripstotheSalty Dog. ill I thank Professor Mark Meisel and Brian Watson for obtaining all ofthe SQUID measurementspresentedinthisdissertation. Icertainlyhaveenjoyedourcollaborationoverthe years,asIfeelIhavegainedagreaterunderstandingofthephysicsbehindsomeoftheproblems wetackleinourchemistryworldandthebenefitsofmultidisciplinaryefforts. PraisetoBrian, whospentcountlesshourstryingtoobtaintransportmeasurementsonsomeoftheoxidizedTTF filmsdiscussedinChapter6priortoourdiscoverythatsuchmeasurementsonthesematerials mightnotnecessarilybepossible. Iamsincerelygratefulforhispains. IappreciateDr.Hitoshi Ohnuki's efforts on obtaining transport measurements on compressed powder samples and SQUIDmeasurementsonmagneticmaterialsduringhisstayhereasavisitingscientist. Hitoshi's Ph.D.dissertationfocusedonconductingTTFLBfilms,andIhavebenefitedgreatlyfromour manyconversations. IgratefullyacknowledgethoseprofessorsandresearchgroupswhoseequipmentIhave "borrowed"atoddtimesthroughoutmystay. IthankProfessorKirkSchanzeforuseofbothhis HewlettPackarddiodearrayspectrophotometerandhisHanovialamp,aswell astheentire Schanzeresearchgroupforenduringthecountlesshoursofnoiseasaresultofthislamp. Lidia Matveevaandthestudentsinthemassspeclabdeserverecognitionfortheirtirelesseffortsin obtainingmassspecanalysesonmyhideouslyinsolublephosphonicacids. Thanksarealso extendedtotheMajorAnalyticalInstrumentationCenterforX-raymeasurementsandtoEric LambersforXPStraining. Specialthankstoeveryoneinthemachine,electronic,andglassshops foralloftheirhelpandeffortsinquicklyfixingthemanyproblemsIhaveencountered. Ialso gratefullyacknowledgetheentirechemistrydepartmentstaff,includingDonnaandLori. Their help,whichhasmademylifeeasier,hasnotgoneunappreciated. IthanktheNSFforfunding, particularlythroughthefellowshipIreceivedmyfirstthreeyearshere. ThepeopleIhavemetthroughoutmytimehereandatCarnegieMellonhavecertainly madethisexperiencemorebearableandentertaining. Myfriendsandourexploitshavekept thingslivelyandinteresting,andImustespeciallythankCraig,Debby,Eve,andJenniferfortheir IV supportandfriendship,especiallythroughalloftheroughpatches. AndofcourseIthankTim forhisversionofcomicrelief. AllofwhatIhaveaccomplishedinthelast27yearswouldnothavebeenpossible withouttheloveandsupportofmymother,Maria. Hergenerosityandselflessnessisunrivaled anywhere,andIamamazedatthegoodfortuneIhavehadinbeingblessedwithherinmylife. I thankJohnforallofhisunfailingloveandsupportandforbecomingpartofourfamily. Ihave enjoyedgettingtoknowhimandhisfamily,includinghisparents,JimandMarian. Iamgrateful tomygrandmother,Margaret,forherprayersandphonecalls,andtomyOma,Elisabetha,forher subliminalmessagesfromabove. ThanksalsotoAuntAggieandUncleDavefortheirconstant supportovertheyears. Ithankmybrother,Bobby,forprovidingsanctuaryformeinsouthFlorida,forallofthe mealsandentertainment,forourtraditionalThanksgivingdinners,andforallofhislove,support, and"good-natured"harassment. Iamalsopleasedtoacknowledgethenewestmembersofthe family,mysister-in-lawSandyandmyniece(andgoddaughter)Emily. IthankMikeforhis wonderfulfriendshipandstaunchsupportovertheyears,evenafterherealizedthatIammuch morethehistoricalscholarthanhe. IameternallygratefultoTom,whoseloveisaconstant sourceofstrengthforme. Iamamazedbyhispatienceandpleasedthatheasksofmenothing morethanIam. Ihopesomedaytoreturnthefavor. TABLEOFCONTENTS Page ACKNOWLEDGMENTS iii LISTOFTABLES ix LISTOFFIGURES x ABSTRACT xvii CHAPTERS 1 MIXEDORGANIC/INORGANICMATERIALS 1 MesoporousMaterials 1 IntercalationCompounds 3 Self-AssembledFilms 5 LayeredMaterials 9 LayeredPerovskites 10 MetalPhosphonates 11 ScopeoftheDissertation 28 2 ZIRCONIUMPHOSPHONATELANGMUIR-BLODGETTFILMS CONTAININGFUNCTIONALORGANICGROUPS 30 ResultsandDiscussion 36 SynthesisandCharacterizationofPhosphonicAcidAmphiphiles 36 LangmuirMonolayers 40 DepositionProcedure 42 X-rayPhotoelectron Spectroscopy 44 X-rayDiffraction 47 AttenuatedTotalReflectanceInfraredSpectroscopy 48 OpticalSpectroscopy 63 StructuralAnalysis 66 Summary 69 ExperimentalSection 70 Synthesis 70 Films 87 VI ANAZOBENZENE-DERIVATIZEDPHOSPHONICACIDFORMSCONTINUOUS LATTICELAYERSWITHDIVALENTANDTRIVALENTMETALIONS 89 ResultsandDiscussion 94 DepositionProcedure 94 CharacterizationofMetalPhosphonateLBFilms 96 StructuralAnalysis 106 MagneticProperties 112 Summary 118 ExperimentalSection 119 Materials 119 SubstratePreparation 120 Instrumentation 120 THERMALANDCHEMICALSTABILITYSTUDIES OFMETALPHOSPHONATELANGMUIR-BLODGETTFILMS 122 Results 125 ThermalStability 125 ChemicalStability 132 Discussion 133 Summary 138 ExperimentalSection 139 Materials 139 SubstratePreparation 139 Instrumentation 140 5 TETRATHIAFULVALENE-FUNCTIONALIZEDMETALPHOSPHONATE SOLIDSANDLANGMUIR-BLODGETTFILMS:STRUCTUREAND MAGNETISM 141 ResultsandDiscussion 145 SynthesisandCharacterization 145 LangmuirMonolayers 150 DepositionProcedure 154 StructuralCharacterization 154 MagneticProperties 175 Summary 189 ExperimentalSection 191 Synthesis 191 Films 201 6 TETRATHIAFULVALENE-FUNCTIONALIZEDMETALPHOSPHONATE LANGMUIR-BLODGETTFILMS:CONDUCTIVITY 204 ResultsandDiscussion 207 IodineasanOxidant 207 CarbonTetrachlorideasanOxidant 214 vu OtherOxidants 232 Summary 235 ExperimentalSection 235 Materials 235 SubstratePreparation 236 Instrumentation 237 TransportMeasurements 239 7 EPILOGUE 241 REFERENCES 244 BIOGRAPHICALSKETCH 257 via LISTOFTABLES Table Page 2-1. IntXePrlSaySeirgnSaplascionfgtsheanZdirRceolnaattievdeTInetmepnlsiattieesLoBftMhoenZoilracyoenrisuamnadnLdBPhBoislpahyoerruFsilms 46 2-2. DichroicRatios,D,ofIRModesandtheCorrespondingMolecularAxisTilt AnglesforZirconatedTemplateLayers 53 2-3. DichroicRatios,D,ofIRModesandtheCorrespondingMolecularAxisTilt AnglesforCappingLayersDepositedontoZirconatedOPATemplates 56 2-4. DichroicRatios,D,ofIRModesandtheCorrespondingMolecularAxisTilt AnglesforCappingLayersintheB4andA4BilayerSamples 60 2-5. TwistAnglesfortheArylMoietieswithintheFilms 68 3-1. DepositionConditionsfortheA4LBBilayers 97 3-2. InterlayerSpacingsMeasuredfromX-rayDiffractionandRelativeIntensitiesofthe MetalandPhosphorusXPSSignalsfortheA4LBBilayerFilms 100 4-1. FilmLossinSingleBilayerSamplesofOctadecylphosphonicAcidandA4with VariousMetals 133 5-1. DepositionConditionsfortheTTFLBBilayers 155 5-2. ExchangeConstants,WeissConstants,andOrderingTemperaturesforTTF- BasedMetalPhosphonateLBFilmsandSolid-StateMaterials 179 IX LISTOFFIGURES Figure Page 1-1. Twoproposedpathwaysforthesynthesisofmesoporousmaterials 2 1-2. ThelayeredstructureofFeOCl 4 1-3. Constructionofmultilayersofalkylsilanederivativesbyself-assembly 7 1-4. Self-assemblyapproachforthefabricationofnoncentrosymmetricthinfilmsofa stillbazoliumderivativeforNLO 8 1-5. Proposedmodelfortheorganizationofazobenzene-terminatedalkylthiolsongold 9 1-6. Crystalstructureof(CioH2iNH3)2CdCl4 10 1-7. (A)Cross-sectionalviewoftwolayersofa-Zr(HP04)2-H20and (B)cross-sectionalviewoftwolayersofy-Zr(P04)(H2P04)H20 12 1-8. Crystalstructureofzirconiumphenylphosphonate 13 1-9. Schematicrepresentationofazirconiumphosphonatematerialcontaining macrocyclicligands 15 1-10.Schematicillustratingtheporousnatureof[(ZrF)2(P04) (03PCH2CH2-bipyridinium-CH2CH2P03)]+X--3H20 16 1-11.Crystalstructureofmanganesephenylphosphonate 16 1-12.Crystal structureofbarium phenylphosphonate 17 1-13.Crystalstructureoflanthanumphenylphosphonate 18 1-14.Schematicillustratingthetopochemicalpolymerizationofdiacetyleneswithinthe metalphosphonatenetwork 20 1-15.Procedurefortheself-assemblyofzirconiumphosphonatefilms 23 1-16.Schematicillustratingthethree-stepprocedurefortheself-assemblyofzirconium phosphonatefilmsofanorientedazobenzenederivativeforSHG 24