Designofmetalorganicframeworkmaterialsbased

UniversityofSouthFloridaScholarCommonsThesesandDissertations6-1-2006Designofmetal-organicframeworkmaterialsbaseduponinorganicclustersandpolycarboxylatesZhenqiangWangUniversityofSouthFloridaThisDissertationisbroughttoyouforfreeandopenaccessbyScholarCommons.IthasbeenacceptedforinclusioninThesesandDissertationsbyanauthorizedadministratorofScholarCommons.Formoreinformation,[e-mail]ng,Zhenqiang,Designofmetal-organicframeworkmaterialsbaseduponinorganicclustersandpolycarboxylates(2006).ThesesandDissertations.Paper2747.:MichaelJ.Zaworotko,Ph.D.MohamedEddaoudi,Ph.D.JulieP.Harmon,Ph.D.DwightA.Sweigart,Ph.D.DateofApproval:November,2006Keywords:crystalengineering,coordinationpolymers,flexibility,ligands,porosity,secondarybuildingunits,supramolecularisomerism,ternarynets,topology©Copyright2006,ZhenqiangWangDedicationTomyfamilyAcknowledgmentsFirstandforemost,IwouldliketoexpressmysincereappreciationtomyadvisorDr.MichaelZaworotkoforhisguidanceandsuggestionsthroughoutthecourseofthiswork.Inaddition,IwouldliketothankDr.MohamedEddaoudi,Dr.JulieHarmon,andDr.DwightSweigart,membersofmysupervisorycommittee,fortheirinvaluablehelps.IwouldalsoliketothankDr.VictorKravtsov,Dr.RosaWalsh,GregMcManusandJasonPermanfortheirhelponcrystallography.MingzhouZhouisgreatlyacknowledgedforhishelpwithNMRexperiments.Finally,IwouldliketothankJohnPerry,TaniseShattock,MirandaCheney,DanielWarrensford,DavidWeyna,SheshankaKesani,andothergroupmembersfortheirhelpfulcommentsandencouragements.Thankyouagainforyoursupport!.iTableofContentsListofTablesvListofFiguresviAbstractxiiChapter1Introduction11.1Preamble:Crystals11.1.1CrystalsandtheScienceofCrystals11.1.2TheCrystalasMolecularEntity31.1.3SolidStateChemistry31.2SupramolecularChemistry51.2.1HistoryandScope51.2.2SupramolecularChemistryinSolution71.3CrystalEngineering:aSupramolecularPerspective101.3.1HistoryandScope101.3.2IntermolecularInteractions121.4Metal-OrganicFrameworks131.4.1HistoryandScope131.4.2DesignPrinciples151.4.3StructuralAnalysisofMetal-OrganicNets18ii1.4.4Metal-OrganicFrameworksasFunctionalMaterials20Chapter2Metal-OrganicFrameworksBaseduponRigidAngularDicarboxylates262.1Introduction262.1.1SecondaryBuildingUnits(SBU’s)262.1.2SupramolecularIsomerism292.1.3HydrogenStorageinMetal-OrganicFrameworks312.2Metal-OrganicFrameworksfromSBUIandBDCorItsDerivatives402.2.1Nanoballs412.2.2Two-DimensionalTetragonalSheetsandKagoméLattices472.2.3Three-DimensionalStructuresandSomePredictedStructures512.3Metal-OrganicFrameworksfromSBUIand1,3-Adamantanedicarboxylate562.4Metal-OrganicFrameworksfromSBUIIandBDCorItsDerivatives582.5Summary632.6Experimental642.6.1Syntheses642.6.2Characterizations66Chapter3Metal-OrganicFrameworksBaseduponaMoreFlexibleDicarboxylates743.1Introduction743.1.1Rigidityvs.Flexibility743.1.2ConformationalAnalysisofOrganicLigands:ACSDSurvey763.2Metal-OrganicFrameworksfromTFBDC793.2.11DStructures793.2.2Guest-DependentSwitch-on/offofTwoTypesofCavitiesin2DiiiStructures813.2.3FunctionalizationofInter-layerCavitiesin2DStructures883.3Summary923.4Experimental933.4.1Syntheses933.4.2Characterizations95Chapter4TopologicalandGeometricalApproachestoMetal-OrganicFrameworks1014.1Introduction:3DNets1014.2TopoligicalAnalysisofMetal-OrganicFrameworks1044.2.1TopoligicalAnalysisofSome3DMOFsfromOurRecentSutdies1044.2.2TopoligicalAnalysisofSome3DMOFsfromtheLiterature1114.3TernaryNets1184.3.1UnitaryNetsandBinaryNets1184.3.2TernaryNets1214.4Summary1304.5Experimental1304.5.1Syntheses1304.5.2Characterizations131Chapter5Metal-OrganicFrameworksBaseduponImide-TypeCarboxylatoLigands1385.1Introduction1385.2DesignofLigandsusingImideReactions1405.2.1Imide-TypeLigandsfromSolutionSynthesis1405.2.2Imide-TypeLigandsfromSolidStateSynthesis144iv5.3Metal-OrganicFrameworksfromPredesignedImide-TypeCarboxylatoLigands1475.3.1Metal-OrganicFrameworksfromLigandL1a1475.3.2Metal-OrganicFrameworksfromLigandL2a1495.3.2.1ExpandedTetragonalSheets1505.3.2.2BilayerStructure1535.4Summary1555.5Experimental1565.5.1Syntheses1565.5.2Characterizations160Chapter6ConclusionsandFutureDirections1686.1SummaryandConclusions1686.2FutureDirections171References173AbouttheAuthor197vListofTablesTable1.1Acomparisonofintermolecularforces.12Table1.2Comparisonofcoordinationsequencesofdiamondandlonsdaleitenets.20Table1.3SelectedmicroporousMOFsthathaveshownadsorptionselectivity.24Table2.1SummaryofhydrogenadsorptioninMOFs.32Table2.2Comparisonofchemicalandstructuralinformationforcompound2,3andtheirparentcompound.50Table2.3Crystallographicdataforthetwothree-dimensionalhypotheticalstructuresH1andH2.54Table2.4Crystallographicdataforcompounds1~8.67Table3.1Crystallographicdataforcompounds9,10a~c,11,12.95Table4.1The11uninodal(10