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RareEarthMetal-OrganicFramework HybridMaterialsforLuminescence ResponsiveChemicalSensors WoodheadPublishingSeriesinElectronicand OpticalMaterials
BingYan
SchoolofChemicalScienceandEngineering,TongjiUniversity,Shanghai, People’sRepublicofChina
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TypesetbySTRAIVE,India
Introductionforrareearthmetal-organic frameworkshybridmaterials 1. Metal-organicframeworks(MOFs),rareearthMOFs, andrareearthfunctionalizedMOFhybridmaterials
1.1Metal-organicframeworks(MOFs)
3
1.1.1Synthesisofmetal-containingnodesorcoordination bondsandlinkerdesignforMOFs3
1.1.2Postsyntheticmodification(PSM)ofMOFs5
1.1.3MOFshybridsorcomposites8
1.1.4PotentialapplicationsofMOFs11
1.2Rareearthmetal-organicframeworks(REMOFs) 22
1.2.1REMOFstructures23
1.2.2SomeapplicationsofREMOFs24
1.3Rareearthfunctionalizedmetal-organicframeworkhybrid materials(REFMOFHs) 26 References 31
2. Rareearthluminescence,MOFsluminescence,rare earthMOFshybridmaterialsluminescence, luminescenceresponse,andchemicalsensing
2.1Rareearthionluminescence 41
2.1.1Atomicspectralterm(2S+1LJ)andenergyleveltransition oftrivalentrareearth(RE3+)ions42
2.1.2Luminescenceandspectroscopyoftrivalentrareearth (RE3+)ions42
2.2Rareearthcomplexmoleculeluminescence 45
2.3MOFsluminescence 49
2.4RareearthMOFshybridmaterialsluminescence 53
2.5LuminescenceforrareearthfunctionalizedMOFshybrid materials 54
2.6Luminescenceresponseforchemicalsensingofrareearth MOFshybridmaterials 63
2.6.1Luminescenceresponseandchemicalsensing inMOFs-basedmaterial63
2.6.2MOFs-basedmaterialsprimarilydisplayspecial advantagesforchemicalsensing66 References 67
PartII Luminescentresponsemodeandsensing mechanismsinrareearthmetal-organic frameworkshybridmaterials 3. Singlemodeforluminescenceresponsivechemical sensinginrareearthmetal-organicframeworkhybrid materials
3.1Introductionforluminescenceresponseofmetal-organic frameworks 75
3.2“Turn-off”luminescenceresponsechemicalsensingforrare earthmetal-organicframeworkhybridmaterials 79
3.3“Turn-On”luminescenceresponsechemicalsensingforrare earthmetal-organicframeworkhybridmaterials 89
3.4“Turn-on-off-on”luminescenceresponsechemicalsensing forrareearthmetal-organicframeworkhybridmaterials 97
3.5Both“Turn-On”and“Turn-Off”luminescenceresponse chemicalsensingondifferentanalytesforrareearthMOF hybridmaterials 103 References 107
4. Dualmodeforratiometricluminescenceresponsive chemicalsensingforrareearthmetal-organic frameworkhybridmaterials
4.1Dualmodeforratiometricluminescence(RL)responsive chemicalsensingofMOFsmaterials 111
4.1.1MOFs’intrinsicdualemission112 4.1.2Single-emissiveMOFswithfluorescentguests114 4.1.3NonemissiveMOFswithencapsulated chromophores115
4.2Dualrareearthionluminescenceforratiometric luminescencesensinginrareearthmetal-organicframework hybridmaterials 116
4.3Ligand(linker)andRE3+ ionsthroughenergytransfer “antennaeffect”forratiometricluminescencesensinginrare earthmetal-organicframeworkhybridmaterials 124
4.4Embeddingadditionalluminescentspeciesforratiometric luminescencesensinginrareearthmetal-organicframework hybridmaterials 132
4.5Singlerareearthfunctionalizedmetal-organicframework hybridmaterialsforratiometricluminescencesensing 136
5. Luminescenceresponsivesensingmechanism inrareearthmetal-organicframeworkhybrid materials
5.1Theluminescenceresponsivesensingmechanism formetal-organicframework-basedmaterials 145
5.1.1Overlapmechanism145
5.1.2Structuralcollapsemechanism147
5.1.3Ionexchangemechanism147
5.1.4Linker-analytesinteractionmechanism148
5.1.5Commonmechanisticpathwaysinvolvedin luminescencesensing148
5.2TheLMETforluminescenceresponseonchemicalsensingin rareearthmetal-organicframeworkhybridmaterials 150
5.3Thephoto-inducedenergytransfer(PET)andfluorescence (F € orster)resonanceenergytransfer(FRET)forluminescence responseforchemicalsensinginrareearthmetal-organic frameworkhybridmaterials 156
5.3.1PETforluminescenceresponseinchemical sensing156
5.3.2FRETforluminescenceresponseinchemical sensing159
5.4Specialinteractionsforluminescenceresponseon chemicalsensinginrareearthmetal-organicframework hybridmaterials 165
5.4.1Hydrogenbondingforluminescenceresponseon chemicalsensing165
5.4.2Coordinationinteractionforluminescenceresponse onchemicalsensing168
5.4.3Reductionreactionforluminescenceresponse forchemicalsensing168
5.4.4Precipitationreactionforluminescenceresponse inchemicalsensing170
References 172
Rareearthmetal-organicframeworkshybrid materialsasluminescenceresponsechemical sensorsfortypicalionicanalytes
6. Rareearthmetal-organicframeworkhybridmaterials forluminescenceresponsivechemicalsensingof metalions(I)
6.1LuminescenceresponsivesensingofFe3+ usingrareearth metal-organicframeworkhybridmaterials 179
6.2LuminescenceresponsivesensingofFe2+ orFe3+/Fe2+ using rareearthmetal-organicframeworkhybridmaterials 186
6.3LuminescenceresponsivesensingofCu2+ usingrareearth metal-organicframeworkhybridmaterials 190
6.4LuminescenceresponsivesensingofZn2+ usingrareearth metal-organicframeworkhybridmaterials 195
6.5Luminescenceresponsivesensingofmultimetalcationsusing rareearthmetal-organicframeworkhybridmaterials 198 References 202
7. Rareearthmetal-organicframeworkhybrid materialsforluminescenceresponsivesensing ofmetalions(II)
7.1LuminescenceresponsivesensingofHg2+ usingrareearth metal-organicframeworkhybridmaterials 209
7.2LuminescenceresponsivesensingofCd2+ usingrareearth metal-organicframeworkhybridmaterials 214
7.3LuminescenceresponsivesensingofPb2+ usingrareearth metal-organicframeworkhybridmaterials 218
7.4LuminescenceresponsivesensingofCr3+ usingrareearth metal-organicframeworkhybridmaterials 220
7.5LuminescenceresponsivesensingofAl3+ usingrareearth metal-organicframeworkhybridmaterials 223
7.6LuminescenceresponsivesensingofAg+ usingrareearth metal-organicframeworkhybridmaterials 226
7.7LuminescenceresponsivesensingofCo2+/Ni2+ usingrare earthmetal-organicframeworkhybridmaterials 228
7.8Luminescenceresponsivesensingoff-blockmetalionsusing rareearthmetal-organicframeworkhybridmaterials 230 References 236
8. Rareearthmetal-organicframeworkhybridmaterialfor luminescenceresponsivechemicalsensingofanions
8.1Rareearthmetal-organicframeworkhybridmaterials forluminescenceresponsivechemicalsensing offluoride(F )ions 243
8.2Rareearthmetal-organicframeworkhybridmaterials forluminescenceresponsivechemicalsensingofother simpleanions(S2 ,HS ,andSCN ) 246
8.3Rareearthmetal-organicframeworkhybridmaterialsfor luminescenceresponsivechemicalsensingofmaingroup elementoxysaltanions 252
8.4Rareearthmetal-organicframeworkhybridmaterialsfor luminescenceresponsivechemicalsensingoftransition metaloxysaltsanions 262 References 272
PartIV Rareearthmetal-organicframeworkshybrid materialsasluminescenceresponsechemical sensorsfortypicalmolecularanalytes
9. Rareearthmetal-organicframeworkhybridmaterials forluminescenceresponsivechemicalsensingof generalmolecules
9.1Rareearthmetal-organicframeworkhybridmaterialsfor luminescenceresponsivechemicalsensingofinorganic molecules 284
9.2Rareearthmetal-organicframeworkforluminescence responsivechemicalsensingofgeneralorganic molecules 300
9.3Rareearthmetal-organicframeworkhybridmaterials forluminescenceresponsivechemicalsensingofgeneral organicpollutantmolecules 312 References 317
10. Rareearthmetal-organicframeworkhybridmaterials forluminescenceresponsivechemicalsensingof specialmoleculespecies
10.1Rareearthmetal-organicframeworkhybridmaterials forluminescenceresponsivechemicalsensing ofbiomolecularspecies 327
10.2Rareearthmetal-organicframeworkhybridmaterials forluminescenceresponsivechemicalsensing ofantibioticsanddrugs 340
10.3Rareearthmetal-organicframeworkhybridmaterials forluminescencesensingofnitroaromaticexplosives(NAE) andotherspecialdangerousspecies 353 References 365
Contents
11. Rareearthmetal-organicframeworkhybridmaterials forluminescenceresponsivechemicalsensingof biomarkers
11.1Biomarkersandtheirchemicalsensing 375
11.2Rareearthmetal-organicframeworkmaterialsfor luminescenceresponsivechemicalsensingof biomarkers 378
11.3Rareearthfunctionalizedmetal-organicframeworkhybrid materialsforluminescenceresponsivechemicalsensingof biomarkers 387 References 405
PartV Rareearthmetal-organicframeworkshybrid materialsasluminescenceresponsechemical sensorsforothersandapplications 12. Rareearthmetal-organicframeworkhybridmaterials forluminescenceresponsivechemicalsensingof temperatureandpHvalue
12.1Rareearthmetal-organicframeworkhybridmaterialsfor luminescencesensingoftemperature 411
12.2Rareearthmetal-organicframeworkhybridmaterialsfor luminescenceresponsivechemicalsensingofpHvalue 432 References 441
13. Molecularlogicgateoperationsofrareearth metal-organicframeworkhybridmaterialsfor luminescenceresponsivechemicalsensing
13.1MolecularBooleanlogicgates 445
13.1.1BasicmolecularBooleanlogicgateoperation446
13.1.2Implementationofatwo-outputcombinational logicgate449
13.1.3Implementationofacascadedlogicgate451
13.1.4Implementationoflogicdevices(4-to-2encoder andparitychecker)451
13.2Luminescenceresponsivesensingofrareearth metal-organicframeworkhybridmaterialsonluminescence forBooleanlogicgates 453
13.3Luminescenceresponsivechemicalsensingofrareearth metal-organicframeworkhybridmaterialsforintelligent molecularsearcherapplications 467 References 479
14. Rareearthmetal-organicframeworkhybridmaterials forluminescenceresponsivechemicalsensing imaging
PartVI
Summaryandprospectforrareearthmetal-organic frameworkshybridmaterialsasluminescence responsechemicalsensors
15. Summaryandprospects
15.1Postsyntheticmodificationtoconstructrareearth metal-organicframeworkhybridmaterials 503
15.2Luminescenceresponsivemodeandchemicalsensing mechanismforrareearthmetal-organicframeworkhybrid materials 506
15.3Luminescenceresponsivechemicalsensingofanalytes forrareearthmetal-organicframeworkhybrid materials 510
15.4Luminescenceresponsivechemicalsensingapplication forrareearthmetal-organicframeworkhybrid materials 513 References 517
Preface Rareearths(REs),asstrategicresourcesofthe21stcentury,haveplayedagreat roleinbothindustryandtheeconomy.Duetotheuniqueelectronicstructure andphysiochemicalpropertiesofrareearthions,theircompoundsareimportant activecandidatesinfunctionalmaterials.Inparticular,rareearthionsdisplay excellentopticalbehaviors,suchassharpemissionspectraforhighcolorpurity, broademissionbandscoveringtheultraviolet(UV)-visible-near-infrared(NIR) region,awiderangeoflifetimesfrommicrosecondstothesecondlevel,high luminescencequantumefficiencies,andsoforth,whichmakesthemahuge treasuryofluminescentmaterials.Inrecentyears,REshaveattractedmuch attentionfortheirwidevarietyofapplicationsinthefieldsoflightingdevices (televisionandcomputerdisplays,opticalfibers,opticalamplifiers,andlasers) andbiomedicalanalysis(medicaldiagnosisandcellimaging).
Metal-organicframeworks(MOFs,alsoknownasporouscoordinationpolymers,orPCPs)areanemergingclassofporousmolecularmaterialsconstructed frommetal-containingnodes(alsoknownassecondarybuildingunits(SBUs)) andorganiclinkers(bridgingligands).Duetotheirstructuralandfunctional tunability,theareaofMOFshasbecomeoneofthefastestgrowingfieldsin chemistry.MOFsembodyversatilefunctionalapplicationsingasstorage,purification,orseparation;heterogeneouscatalysisorphotocatalysis;optic, electronic,ormagneticmaterialsordevices;aswellasbiomedicinesorbioimages.Certainly,MOFsareemployedasaplatformforluminescentmaterials basedontheirintrinsicopticalandphotonicpropertiesofmetalionsandorganic ligands,orguestspeciescollaborativelyassembledand/orencapsulatedinto theirframeworks.TheabundantluminescentresponsiveperformanceofMOFs providestheirgreatpotentialinchemicalsensing.
Rareearthmetal-organicframeworkhybridmaterialscombinethevirtuesof bothMOFmaterialsandrareearthions,whichcancreatenovelpropertiesas wellasfunctionalandphotofunctionalapplications.Inparticular,withrare earthionfunctionalizedMOFhybridmaterials,luminescentRE3+ ionsare incorporatedintoMOFhostswithlittlecontent,andthecharacteristicemission ofRE3+ isobtained.Thisisidenticaltothetraditionalrareearthiondopedphosphors.JustlikepureluminescentrareearthMOFmaterials,RE3+ canproduce an“antennaeffect”andcauseapronouncedincreaseintheluminescenceintensitythroughtheintramolecularenergytransferprocessfromlinkerstoRE3+.In addition,therelativelylimitedcontentofhybridmaterialsoftenallowsthe
existenceofluminescenceoforiginallinkersorMOFsthemselvesifthefunctionalizedamountofRE3+ iscontrolledappropriately.Thismakeitpossibleto exhibitmultiplecenterluminescenceforthesamehybridsystemandevenrealizeluminescencecolortuningorwhiteluminescenceintegration.Withregard tointegrity,thepurerareearthMOFmaterialsareconsideredinthisbook.Thus rareearthMOFhybridmaterialsencompasstwomainaspects:oneisthepure rareearthMOFs,andtheotherisrareearthfunctionalizedMOFhybrid materials.
Thisbookconsistsof6parts,coveredin15chapters.Thefirstpart(Chapters 1and2)isageneralintroductiontoMOFs,rareearthMOFs,andrareearthfunctionalizedMOFhybridmaterials(Chapter1);andrareearthluminescence, MOFluminescence,rareearthMOFluminescence,aswellasluminescence responseandchemicalsensing(Chapter2).Thesecondpart(Chapters3,4, and5)givesanoverviewoftheluminescentresponsemodeandsensingmechanismsinrareearthmetal-organicframeworkhybridmaterials:singleluminescentmodesensing(1D)(Chapter3),dualluminescentmode(2D)for ratiometricsensing(Chapter4),andluminescentresponsivesensingmechanisms(Chapter5).Thethirdpart(Chapters6,7,and8)shedslightonrareearth metal-organicframeworkhybridmaterialsasluminescenceresponsechemical sensorsfortypicalionicanalytes,metalcations(I)(Chapter6),(II)(Chapter7), andanions(Chapter8).Thefourthpart(Chapters9,10,and11)focusesonrare earthmetal-organicframeworkhybridmaterialsasluminescenceresponse chemicalsensorsformolecules:generalmolecularchemicals(Chapter9),specialorganicmolecules(Chapter10),andbiomarkers(Chapter11).Thefifthpart (Chapters12,13,and14)involvesrareearthmetal-organicframeworkhybrid materialsasluminescenceresponsechemicalsensorsforotherapplications: includingtemperatureandpHvalue(Chapter12),logicgateoperations (Chapter13),andimagingapplications(Chapter14).Thesixthpart (Chapter15)givesasummaryandprospectforrareearthMOFhybridmaterials asluminescenceresponsechemicalsensors.
Finally,IwanttoexpressmysinceregratitudetomyPhDandmaster’sstudents,whoseresearchworkmakesupthemaincontentofthisbook.Ialsowish toshowmyappreciationtomycolleagues,especiallytothescholarsinthe researchfieldsofrareearthmetal-organicframeworks,whichisanimportant componentofthisbook.Manycolleaguescholarshaveprovidedvaluable reviewsoftherelevanttopicsfortheinstructionandoutlineofthisbook.Ihope thatthisbookwillprovidereaderswithinsightsintotherecentdevelopmentsof rareearthmetal-organicframeworkhybridmaterialsforluminescentresponsivechemicalsensing.
PartI Introductionforrareearth metal-organicframeworks hybridmaterials Metal-organicframeworks (MOFs),rareearthMOFs,and rareearthfunctionalizedMOF hybridmaterials 1.1Metal-organicframeworks(MOFs) Metal-organicframeworks(abbreviatedasMOFsandalsoknownasporous coordinationpolymers(PCPs))areaclassofporouspolymericmolecularmaterials,consistingofmetalionnodesconnectedtogetherbyorganicbridging ligands(linkers)(Schemein Fig.1.1),whichareanewdevelopmentintheinterdisciplinaryfieldofcoordinationchemistryandfunctionalmaterials [1–3]. Duetotheirstructuralandfunctionaltunability,MOFshavebecomeoneof thefastestgrowingresearchfieldsininorganicchemistry.TheessenceofMOFs chemistryisthattheframeworksareassembledbylinkingmolecularunitsof well-definedshapesbychemicalbondsintoperiodicframeworks.Animportant componentofreticularchemistryisthedeconstructionofsuchstructuresinto theirunderlyingnetstofacilitatedesignedsynthesisofmaterialswithtargeted porosity,poresize,andfunctionality.TheorganicligandsofMOFsgivethem flexibilityanddiversityintheirchemicalstructuresandfunctions.Thesynthesis ofMOFshasattractedextensiveattentionduetothepossibilityofobtaininga largevarietyofinterestingstructuresforarangeofapplicationsrelatedto porousmaterials [4–8].TheexplorationofMOFsmainlyinvolvesfourcategories:(1)synthesisofmetal-containingnodesorcoordinationbondsandlinker designforMOFs;(2)postsyntheticmodification(PSM)ofMOFs;(3)MOF hybridsorcomposites;and(4)potentialapplicationsofMOFs.
1.1.1Synthesisofmetal-containingnodesorcoordinationbonds andlinkerdesignforMOFs
InMOFsstructures,anoderepresentsaparticularenvironment(tetrahedra, octahedra,etc.)connectedtoafixednumberofrelatedpoints,whichdepends onthegeometry(tetrahedral ¼ 4,octahedral ¼ 6,cubic ¼ 8).Theirstructurescan thenberepresentedmathematicallyaseitheradiscrete(zero-dimensional—0D)
RareEarthMetal-OrganicFrameworkHybridMaterialsforLuminescenceResponsiveChemicalSensors https://doi.org/10.1016/B978-0-323-91236-5.00003-7 Copyright © 2022ElsevierLtd.Allrightsreserved. 3
4 PART I Introductionforrareearthmetal-organicframeworkshybridmaterials
FIG.1.1 ConceptualillustrationofstructuringofMOFsatmicroscopic/mesoscopicscales.The assemblyofmetalionswithorganicligandsconstructsmolecularframeworkstructures. (ReproducedwithpermissionfromS.Furukawa,J.Reboul,S.Diring,K.Sumida,S.Kitagawa,Structuring ofmetal-organicframeworksatthemesoscopic/macroscopicscale.Chem.Soc.Rev.43 (2014)5700–5734.Copyright2014RoyalSocietyofChemistry.)
oraninfinite(one-dimensional—1D),two-dimensional—2D),andthreedimensional—3D))periodicarrangementasanextendedrepresentationof thenodes.Thusthetopologyofanetdependsonthenumberofnodesinaparticularstructure.AsimplifieddescriptionofMOFsstructurewillbeconsidered asametalcenterormetalclusterofionsconnectedbyanorganiclinker.To derivethevertexsymbolandthecorrecttopologyforsuchstructures,itis importanttoidentifythenodesaccordingtocoordinationchemistry principles [9].
TounderstandMOFsstructures,thenodeandthenetconceptareusedto describethevertexsymbolsinsome2Dand3Dsystems. (1)3Dstructures. (a)Uninodalstructures arebasedononlyonetypeofnode,whichhave3(trigonal),4(squareplanar,tetrahedral),5(trigonalbipyramidal),6(octahedral),8 (cubic),andotherhigher(10or12)connectednodes. (b)Binodalstructures havetwogeometricallydifferentnodesinaMOFsconstitutes,formedusing trigonal-tetrahedral;tetrahedral-squareplanar;tetrahedral-octahedraland tetrahedral-cubicnodes. (2)2Dstructures.MOFswith2Dlayerstructures canbedescribedusingnodalconnectivity. (a)Uninodalstructures contain 3connectednodes,4connectednodes,5connectednodes,and6connected nodes,respectively. (b)Binodalstructures inthecontextofthetopologyof MOFsbasedoncommongeometricalnodesarerare,althoughsometopologies canbeobtainedbasedontrigonal-octahedralnodes. (3)3DMOFsbasedon2D layers.The3DMOFswith2Dnetworktopologiesarepillaredbyrigidlinkers, whichcanhaveeitherasimpleuninodalstructureorabinodalstructurewithin thelayersusingtheorganicligandsasthelinker.Eitherthesameligandora completelydifferentorganiclinkercanbeusedtoarriveatthe3Dstructure. (4)Zeoliticimidazolateframeworks(ZIFs).Imidazoleasthesimplemoleculehasanidealpositionbetweenthenitrogenatomsinthestructures,and behavesasalinkerbetweenthemetalcenters,addressingtheconcernsofcharge neutrality.Themostimportanttopologybasedonthetetrahedralnodeisthediamondtopology.TheseZIFcompoundshavebeenextensivelypreparedfor mimickingzeolitetopologies [9–16]
Ontheotherhand,thetermMOFsoriginatedfromitssecondarybuilding units(SBUs)asclustersbuiltentirelywithcovalentbonds [17–22].
ThesynthesisofSBUscanbeusedtodirecttheassemblyoforderedframeworkswithrigidorganiclinkers,whichmakesithighlypossibletopredict thechemistryoftheyieldedcrystallinematerials [17–30].Theorientationof organiclinkerswillresultintheassemblyofMOFswithpredeterminedstructuraltopologies [23–30].Generally,bothSBUs(asconnectors)andorganic ligands(aslinkers)combinetodeterminethefinalframeworktopology. (1) Ditopiccarboxylatelinkers.Theselinkerspossessbothreadyaccessibility andeasilyperceivablestructuresincombinationwithdifferentSBUs:4connectedpaddlewheelclusters,6-connectedoctahedralclusters,6-connected trigonal-prismaticclusters,12-connectedclusters,andinfinitechainclusters, respectively. (2)Tritopiccarboxylatelinkers.Theselinkersarerelatedtodifferentclusters:4-connectedpaddlewheelclusters,6-connectedoctahedralclusters,6-connectedtrigonal-prismaticclusters,andmultipleSBUs. (3) Tetratopiccarboxylatelinkers.Theselinkersappeartobeveryintriguing buildingunitsinMOFsconstructions,especiallythosewithtetrahedralgeometry.Tetrahedralcarboxylatelinkersarerelatedtodifferentclusters:8-connected cubicalclusters,4-connectedsquareplanarclusters,8-connectedhexagonalbipyramidalclusters,andnonregulartetrahedralcarboxylatelinkers. (4)Hexatopic carboxylatelinkers.Theselinkersarerelatedto1,3-atedbenzenedicarboxylate units,4,40 -azanediyldibenzoateunitsand1,10 :30 ,100 -terphenyl-4,400 -dicarboxylate units. (5)Octatopiccarboxylatelinkers.MOFswiththeselinkersarestillrare, possiblyduetothesyntheticchallengesinthelinkersthemselves,whoseframeworksarebasedonlinkerswithlongarmsthattendtoforminterpenetratedstructures. (6)Mixedlinkers.Theycontainfourtypes:ditopic-ditopiclinearlinkers, tritopiccarboxylate-ditopiccarboxylatelinkers,carboxylate-pyridinelinkers,and linkerscoordinativelyidenticalbutwithdistinctshapes. (7)Desymmetrized linkers (8)Metallo-linkers.Thesemainlyinvolvefourtypeswithdifferent donors:OandSdonors,NandPdonors,Cdonors,andmixeddonorgroups. (9)N-heterocycliclinkers.OrganiclinkerscontainingNdonors,suchaspyridine andazolederivatives,haveachievedstableMOFsviaN-metalcoordination, includingditopicN-heterocycliclinkersandpolytopicN-heterocyclic linkers [23].
1.1.2Postsyntheticmodification(PSM)ofMOFs Postsyntheticmodifications(PSMs)areparticularlyattractiveforusewith MOFsmaterialsforavarietyofreasons. (I) ThesolvothermalreactionconditionstopreparemostMOFsgreatlylimitthetypesoffunctionalgroupsthatcan befunctionalizedbyPSM. (II) TheorganicligandsinMOFsopenthepossibilityofemployingawiderangeoforganictransformations. (III) MOFs’porous structuresallowreagentstoaccesstheinteriorofthesolidsfortheirfunctionalization [31–44].ThusvariousfunctionscanbeimpartedtoMOFsbyincorporatingdifferentpartsoftheMOFstructure,includingmetalions/clusters, organiclinkers,andemptyspacesinsidethecavities(Fig.1.2,left).Avariety
FIG.1.2 Schematicdepictionoffunctionalization (left) andPSMstrategies (right) ofMOFs:postsyntheticmodification(PSM),postsyntheticdeprotection(PSD), postsyntheticexchange(PSE),postsyntheticinsertion(PSI),andpostsyntheticpolymerization(PSP).SBUsarerepresentedasgoldspheres,andligandstrutsare representedby gray rods. (ReproducedwithpermissionfromS.A.A.Razavi,A.Morsali,Linkerfunctionalizedmetal-organicframeworks.Coord.Chem.Rev. 399(2019)213023andS.M.Cohen,Thepostsyntheticrenaissanceinporoussolids.J.Am.Chem.Soc.139(2017)2855 2863.Copyright2019Elsevierand 2014AmericanChemicalSociety.)
oforganicfunctionalgroupsarefunctionalizedtotuneandoptimizethehostguestchemistryofMOFs,whichisapracticalandrationalstrategytoimprove MOFefficiencyindifferentapplications.Moreover,functionalizationalsohas crucialinfluencesonthestructuralpropertiesofMOFs,suchascrystallinity, porosity,flexibility,stability,andtopologythroughinducedstructuralchanges anddifferenttypesofsecondaryinteractions.Subsequently,itispossibletosynthesizefunctionalMOFsandtheirhybridmaterialsusingPSM [42]
(1) RequirementsforPSM.MOFsrequirethefollowingparameters: (a) Beingsufficientlyporoustoallowaccessofallrequiredreagentstothe interiorofthelattice. (b) Possessinganavailablefunctionalgroupto undergoachemicaltransformation. (c) Beingstabletothereactionconditions. (d) Beingstabletoanybyproductsproducedbythereactionconditions.Todate,thechoicesofbothMOFsandreactiongovernthescopeof transformationsthatcanberealizedbyPSM.
(2) TypesofPSM.Broadlyspeaking,anychangeofthecompositionorstructureofMOFsmaybeconsideredaformofPSM,suchasthedesolvationor activationofMOFs,theexchangeofguestspeciesfromMOFs,theinclusionorencapsulationphenomenaofbeingperformedinaPSMmanner, etc.Inanarrowsense,however,itisimportanttodefinethedifferenttypes ofPSMtodistinguishthesechemicalreactionsfromthepreviouslymentionedroutinehandlingandguestinclusionphenomenaofMOFs.PSMof MOFscanbedividedintothreeareas:(a)covalentPSM,(b)dativePSM (coordinatecovalentPSM),and(c)postsyntheticdeprotection(PSD) (Fig.1.2,right).Thetypeofchemicalbondthatisformedorbrokenduring thePSMapproachdistinguisheseachofthesemethods.Itisimportantto notethatthesedifferentPSMmethodsarenotmutuallyexclusive,andperhapsutilizeacombinationofstrategiestoobtainmaterialsofhighcomplexityandfunctionality.Inadditiontoachievingthedesiredchemical transformation,itisimportantthattheMOFscannotbedestroyedunder thereactionconditions.Indeed,PSMmethodsareintendedtoproduce novelhybridmaterialsthatretainthecharacteristicfeaturesofMOFs [36].
(1)CovalentPSM.Thisisdefinedastheuseofareagenttomodifyacomponent oftheMOFsinaheterogeneous,postsyntheticmannertoformanewcovalent bond,whosetargetisgenerallytheorganiclinkeroftheMOFs.Currently,covalentPSMisthemostextensivelyinvestigatedofthedifferentPSMmethods,and isproventobeapowerfulandversatilemethodforintroducingabroadrangeof chemicalgroupsintoMOFs. (2)DativePSM.Thistypeisdefinedastheuseofa reagentthatformsadativebondwithacomponentoftheMOFsinaheterogeneous,postsyntheticmanner.Notonlycanaligandbeaddedtotheframeworkto coordinatetotheSBUoftheMOFs,butalsoametalsourcecanbeaddedtothe MOFstobindtotheorganiclinkeroftheMOFs,occurringthroughtheformation ofdativebonds. (3)PSD.ThisreactionisperformedontheMOFsina postsyntheticmannerresultinginthecleavageofachemicalbondwithinanintact
framework.Inprinciple,anykindofchemicalbondcanbebrokenduringaPSD reactiontorevealachemicalfunctionalityandproducematerialswithdifferent properties.WithinsomehighlystableMOFs,boththeeliminationandadditionof multitopiclinkersormetalionsarepossiblewithoutdestructionoftheframework. (4)Postsyntheticmetalexchange(PSME).Cationdopingisalsowidely employedinnanocrystalstotunetheirproperties. (5)Postsyntheticligand exchange(PSLE).Thisrepresentstheexchangeofthekeyextendingligand ofaframeworkbyanothersimilarligandofdifferentlengthorfunctionalgroup, withtheretentionoftheMOFstopology. (6)Postsyntheticeliminationand installation(PSE&I).Somelinkersconstitutingtheframeworkcanbeeliminatedwithcoordinationchangesinthemetalclusterbutpreservationoftheinfiniteframeworkconnection.Ifthecoordinationsiteoftheadjacentmetalcluster matcheswellwithanadditionallinker,PSImaysucceedincreatinganewMOFs withhigherconnectionnumbers. (7)TandemPSM.ThistypeisusedinproducingMOFswithmultiplefunctionalitiesotherwisedifficultorinfeasibletoacquire bydirectsyntheticmethods. (i)Engineeringporosityandporesbytandem PSM.Bothincreasedanddecreasedporositycanbeobtaineddependingon thesizeandspatialconfigurationofthemodifiedgroups,whosechangeinporosityismoderateandlimitedbytheconstanttopologyoftheframework. (ii) ImprovingstructuralstabilitybytandemPSM.Thedirectintroductionoftargetmetalionsmaybesubjectedtolowexchangerate,uncompletedconversion, decompositionoftheMOFs,andothers.Basedontheexchangingmechanismof differentmetalions,tandemPSMEisusefulforimprovingstructuralstability. (iii)ModifyingsurfaceandinteriorbytandemPSM.Basedonthereactivity andspatialeffectwithintheconfinedchannels,thetraditionaldesignofthereactionpathwaysprovidesachancetoengineereitherthesurfaceortheinteriorof MOFs(Fig.1.2,right) [31–44]
1.1.3MOFshybridsorcomposites InordertosatisfythepracticalapplicationsofMOFs,itisdesirabletofurther enhancetheirpropertiesandcreatenewfunctionalities.MOFscomposites/ hybridsarematerialscomposedofoneMOFsandoneormoredistinctconstituentmaterials,includingotherMOFs,withpropertiesnoticeablydifferentfrom thoseoftheindividualcomponents.Incompositeorhybridmaterials,the advantagesofbothMOFs(structuraladaptivityandflexibility,highporosity withorderedcrystallinepores)andvariouskindsoffunctions(optical,electrical,magnetic,andcatalyticproperties)canbecombinedeffectively,accessing newphysicalandchemicalpropertiesalongwithenhancedperformancethatis notattainablewiththeindividualcomponents.Consequently,theremarkable featuresofcompositesorhybridsresultingfromthesynergisticcombination ofbothMOFsandotheractivecomponentsmakethemsuitableforawiderange ofapplications.Todate,MOFshybrids/compositeshavebeenmadewithversatileactivespecies,includingmetalnanoparticles/nanorods(NPs/NRs), oxides,quantumdots(QDs),polyoxometalates(POMs),polymers,graphene, 8 PART I Introductionforrareearthmetal-organicframeworkshybridmaterials
FIG.1.3 TheschemeforthecompositesofMOFsandfunctionalmaterials. (Reproducedwith permissionfromQ.Zhu,Q.Xu,Metal-organicframeworkcomposites.Chem.Soc.Rev.44 (2014)5468 5512.Copyright2014RoyalSocietyofChemistry.)
carbonnanotubes(CNTs),dyes,biomolecules,andsoon,resultinginperformanceunattainablebytheindividualconstituents(Fig.1.3).Moreover,these hybridsorcompositesofferthegreatadvantageofflexibleandoptimumdesign, whichisdesirabletoharnesstheusefulpropertiesthroughtheincorporationof variouskindsoffunctionalmaterialsintoMOFs [45–65]
(1) MOFs-metalormetaloxideNPcomposites.PorousMOFsarethermallyrobustandhavepermanentnanoscalecavitiesoropenchannelsthat providepowerfulconfinementeffects,whichcanbeutilizedassupports formetalNPswithcontrolledsizesinsidethepores,therebycircumventingthecommonissueofNPaggregationandbenefitingtheirutilizationin applications.Inaddition,someattemptshavebeenundertakentointegrate metaloxides(especiallythosewithmagneticorsemiconductingproperties)andMOFsintocore-shellnanostructures [45–53].
(2) MOFs-silicacomposites.TherearecurrentlytwomaintypesofMOFssilicacomposites: (a) incorporatingdispersedsilicaNPswithinthepores/ channelsofMOFsorgrowthofaMOFsshellonapreformedsilicasphere inMOFsprecursorsolutions(SiO2@MOFs); (b) usingasilicashellasa surfacecoatingorthemesoporouspropertiesandprocessabilityofsilica supportstopromotethegrowthofmicroporousMOFsparticlesthroughouttheporoussilicasupports(MOFs@SiO2) [45,54]
(3) MOFs-organicpolymercomposites.Confinedpolymersatnanometer scalesexhibitfascinatingandunexpectedpropertiesdifferentfromthose inthebulkstate.MOFs-organicpolymercompositesformedfromvarious combinationsofMOFsandorganicpolymerscanconstituteaclassof compositematerialswithcombinedproperties [45,55]
(4) MOFs-QDscomposites.TheversatilityoffunctionalMOFscanbe extendedbyintroducinghighlyluminescentsemiconductorQDswithin theframeworksofMOFs.InQD@MOFscomposites,QDscanbestabilizedagainstphotochemicaldegradationthroughthedepositionofananometerMOFsshell,whileretainingtheirvaluableopticalproperties [45].
(5) MOFs-POMcomposites.ThedispersionofPOMswithinMOFspreventsthePOMsfromconglomeratinganddeactivating.InsuchPOMbasedMOFs,theorganicligandssubstitutefortheoxogroupsofPOMs tocovalentlylinkthemetalliccenters.What’smore,POMscanbeencapsulatedintheporesofMOFsthroughhost-guestinteractionstoform POM@MOFscomposites [45]
(6) MOFs-carboncomposites.Theexceptionallymechanical,electrical, andthermalpropertiesofcarbonmaterials(grapheneandCNTs)commendthemasvaluablenanostructuredfillersinMOFcomposites.NumerousMOFs-nanocarboncompositeshavebeenmadewithactivated carbons,carbonmonoliths,grapheneoxide(GO),andCNTs,andhave beenintensivelyexploredfordiverseapplications [45].
(7) MOFsthinfilmsonsubstrates.Thedepositionofpatternedthinfilmsof MOFsonasubstratehaspavedthewayforthenanotechnologicalapplicationsofMOFs-baseddevices.Generally,twofabricationmethodshave beendistinguishedforthedirectgrowth/depositionofMOFsthinfilms: (a) ThesubstrateisaddedtoaMOFssynthesissolutionunderambient orsolvothermalconditions,growingonthesurfaceofthesubstrateand sometimesinsolutionatthesametime.Thisgrowthleadstotheformation ofpolycrystallinefilmswherecrystalsareattachedtothesubstratesurfaceinanintergrownandcontinuousfashion. (b) Thelayer-by-layer (LBL)methodwasdevelopedforthefacilepreparationofMOFsthin filmsonthesubstratesandreferredtoasliquidphaseepitaxy.Thistechniquereliesonthesequentialdepositionofmonolayersofmetalsaltsand organiclinkersonafunctionalizedsubstrate.TheLBLmethodpermits thegrowthofsmoothandhomogeneousMOFsultrathinfilmswithdiametersinthenanometerrange,whichachievegoodcontroloverthethickness,crystallographicorientation,andinterpenetrationoftheMOFs multilayers [45,56–59].
(8) MOFs@MOFscore-shellheterostructures.Theconstructionofmultifunctionalcore-shellheterostructuresinvolvestwostrategies. (a) HeteroepitaxialgrowthofashellMOFscrystalontheexternalsurfaceofanother seedMOFscrystalcouldgenerateacompositecrystal,inwhichthetwo coordinationcomponentsaresegregatedintodifferentregionsofthecrystal.Thisapproachisbasedonaclosecrystallatticematchbetweenthe underlyingMOFssubstrateandthedepositedMOFs. (b) PSMstrategies includetheselectivereactionofthereactiveresidueofanorganiclinker andthecontrolledreplacementoftheframeworkmetalionsorligands, whosemodificationisselectivelyconstrainedtoeithertheexternalsurfaceortheinternalcoreoftheMOFscrystals [45].
(9) MOFs-enzymecomposites.ThetunablebutuniformporesizesandfunctionalizableporewallsofporousMOFsmaymakethemappealingto accommodateenzymesforcatalyticapplications.Nevertheless,the microporesizeofmostMOFsprecludestheentryoflarge-sizedenzymes
Chapter 1 11
andcanresultinonlyexternalsurfaceattachmentwithlowenzymeloadingviaadsorptionand/orcovalentbondingreaction [60–65]
(10) MOFs-othermolecularspeciescomposites.Molecularmaterialssuchas organicdyes,organometalliccompounds,metalloporphyrins,biomolecules, andotherfunctionalmoleculescanalsobecomposedwithMOFsforvarious applications.TheuseofMOFsasmolecularencapsulatorstakesadvantage oftheirpowerfulconfinementeffectto protectmoleculesfromaggregation, heterogeneousdistribution,andleaching.Impregnationproceduresare mostlyusedtoencapsulatethesemolecularmaterials.Inaddition,the self-assemblyofMOFsinthepresenceofmolecularmoietiesintheMOFs precursorsolutionscanleadtoirreversiblein-situencapsulation [45]
1.1.4PotentialapplicationsofMOFs MOFshaveuniquepropertiesaswellasanextraordinarydegreeofvariability forboththeorganic(ligands)andinorganic(metalionsorclusters)components oftheirstructures,makingthemofinterestforpotentialapplicationsinpractical fields(Fig.1.4).Withtheinputofindustrialpartners,someofthesepromising MOFsforimportantapplicationswillsoonbeimplementedinourdailylives [66–71].
FIG.1.4 GraphicillustrationofporeandfunctionengineeringtodevelopmultifunctionalMOF materials. (ReproducedwithpermissionfromB.Li,H.Wen,Y.Cui,W.Zhou,G.Qian,B.Chen, Emergingmultifunctionalmetal-organicframeworkmaterials.Adv.Mater.28(2016)8819–8860.Copyright2016Wiley.)
