Table Of ContentRare Earth Metal-Organic Framework
Hybrid Materials for Luminescence
Responsive Chemical Sensors
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Woodhead Publishing Series in Electronic and
Optical Materials
Rare Earth Metal-Organic
Framework Hybrid
Materials for Luminescence
Responsive Chemical
Sensors
Bing Yan
SchoolofChemicalScienceandEngineering,TongjiUniversity,Shanghai,
People’s Republicof China
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Contents
Preface xiii
Part I
Introduction for rare earth metal-organic
frameworks hybrid materials
1. Metal-organic frameworks (MOFs), rare earth MOFs,
and rare earth functionalized MOF hybrid materials
1.1 Metal-organicframeworks(MOFs) 3
1.1.1 Synthesisofmetal-containingnodesorcoordination
bondsandlinkerdesignforMOFs 3
1.1.2 Postsyntheticmodification(PSM)ofMOFs 5
1.1.3 MOFshybridsorcomposites 8
1.1.4 PotentialapplicationsofMOFs 11
1.2 Rareearthmetal-organicframeworks(REMOFs) 22
1.2.1 REMOFstructures 23
1.2.2 SomeapplicationsofREMOFs 24
1.3 Rareearthfunctionalizedmetal-organicframeworkhybrid
materials(REFMOFHs) 26
References 31
2. Rare earth luminescence, MOFs luminescence, rare
earth MOFs hybrid materials luminescence,
luminescence response, and chemical sensing
2.1 Rareearthionluminescence 41
2.1.1 Atomicspectralterm(2S+1L)andenergyleveltransition
J
oftrivalentrareearth(RE3+)ions 42
2.1.2 Luminescenceandspectroscopyoftrivalentrareearth
(RE3+)ions 42
2.2 Rareearthcomplexmoleculeluminescence 45
2.3 MOFsluminescence 49
2.4 RareearthMOFshybridmaterialsluminescence 53
2.5 LuminescenceforrareearthfunctionalizedMOFshybrid
materials 54
v
vi Contents
2.6 Luminescenceresponseforchemicalsensingofrareearth
MOFshybridmaterials 63
2.6.1 Luminescenceresponseandchemicalsensing
inMOFs-basedmaterial 63
2.6.2 MOFs-basedmaterialsprimarilydisplayspecial
advantagesforchemicalsensing 66
References 67
Part II
Luminescent response mode and sensing
mechanisms in rare earth metal-organic
frameworks hybrid materials
3. Single mode for luminescence responsive chemical
sensinginrareearthmetal-organicframeworkhybrid
materials
3.1 Introductionforluminescenceresponseofmetal-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
3.5 Both“Turn-On”and“Turn-Off”luminescenceresponse
chemicalsensingondifferentanalytesforrareearthMOF
hybridmaterials 103
References 107
4. Dual mode for ratiometric luminescence responsive
chemical sensing for rare earth metal-organic
framework hybrid materials
4.1 Dualmodeforratiometricluminescence(RL)responsive
chemicalsensingofMOFsmaterials 111
4.1.1 MOFs’intrinsicdualemission 112
4.1.2 Single-emissiveMOFswithfluorescentguests 114
4.1.3 NonemissiveMOFswithencapsulated
chromophores 115
4.2 Dualrareearthionluminescenceforratiometric
luminescencesensinginrareearthmetal-organicframework
hybridmaterials 116
Contents vii
4.3 Ligand(linker)andRE3+ionsthroughenergytransfer
“antennaeffect”forratiometricluminescencesensinginrare
earthmetal-organicframeworkhybridmaterials 124
4.4 Embeddingadditionalluminescentspeciesforratiometric
luminescencesensinginrareearthmetal-organicframework
hybridmaterials 132
4.5 Singlerareearthfunctionalizedmetal-organicframework
hybridmaterialsforratiometricluminescencesensing 136
References 140
5. Luminescence responsive sensing mechanism
in rare earth metal-organic framework hybrid
materials
5.1 Theluminescenceresponsivesensingmechanism
formetal-organicframework-basedmaterials 145
5.1.1 Overlapmechanism 145
5.1.2 Structuralcollapsemechanism 147
5.1.3 Ionexchangemechanism 147
5.1.4 Linker-analytesinteractionmechanism 148
5.1.5 Commonmechanisticpathwaysinvolvedin
luminescencesensing 148
5.2 TheLMETforluminescenceresponseonchemicalsensingin
rareearthmetal-organicframeworkhybridmaterials 150
5.3 Thephoto-inducedenergytransfer(PET)andfluorescence
(Fo€rster)resonanceenergytransfer(FRET)forluminescence
responseforchemicalsensinginrareearthmetal-organic
frameworkhybridmaterials 156
5.3.1 PETforluminescenceresponseinchemical
sensing 156
5.3.2 FRETforluminescenceresponseinchemical
sensing 159
5.4 Specialinteractionsforluminescenceresponseon
chemicalsensinginrareearthmetal-organicframework
hybridmaterials 165
5.4.1 Hydrogenbondingforluminescenceresponseon
chemicalsensing 165
5.4.2 Coordinationinteractionforluminescenceresponse
onchemicalsensing 168
5.4.3 Reductionreactionforluminescenceresponse
forchemicalsensing 168
5.4.4 Precipitationreactionforluminescenceresponse
inchemicalsensing 170
References 172
viii Contents
Part III
Rare earth metal-organic frameworks hybrid
materials as luminescence response chemical
sensors for typical ionic analytes
6. Rare earth metal-organic framework hybrid materials
for luminescence responsive chemical sensing of
metal ions (I)
6.1 LuminescenceresponsivesensingofFe3+usingrareearth
metal-organicframeworkhybridmaterials 179
6.2 LuminescenceresponsivesensingofFe2+orFe3+/Fe2+using
rareearthmetal-organicframeworkhybridmaterials 186
6.3 LuminescenceresponsivesensingofCu2+usingrareearth
metal-organicframeworkhybridmaterials 190
6.4 LuminescenceresponsivesensingofZn2+usingrareearth
metal-organicframeworkhybridmaterials 195
6.5 Luminescenceresponsivesensingofmultimetalcationsusing
rareearthmetal-organicframeworkhybridmaterials 198
References 202
7. Rare earth metal-organic framework hybrid
materials for luminescence responsive sensing
of metal ions (II)
7.1 LuminescenceresponsivesensingofHg2+usingrareearth
metal-organicframeworkhybridmaterials 209
7.2 LuminescenceresponsivesensingofCd2+usingrareearth
metal-organicframeworkhybridmaterials 214
7.3 LuminescenceresponsivesensingofPb2+usingrareearth
metal-organicframeworkhybridmaterials 218
7.4 LuminescenceresponsivesensingofCr3+usingrareearth
metal-organicframeworkhybridmaterials 220
7.5 LuminescenceresponsivesensingofAl3+usingrareearth
metal-organicframeworkhybridmaterials 223
7.6 LuminescenceresponsivesensingofAg+usingrareearth
metal-organicframeworkhybridmaterials 226
7.7 LuminescenceresponsivesensingofCo2+/Ni2+usingrare
earthmetal-organicframeworkhybridmaterials 228
7.8 Luminescenceresponsivesensingoff-blockmetalionsusing
rareearthmetal-organicframeworkhybridmaterials 230
References 236
8. Rareearthmetal-organicframeworkhybridmaterialfor
luminescenceresponsivechemicalsensingofanions
8.1 Rareearthmetal-organicframeworkhybridmaterials
forluminescenceresponsivechemicalsensing
2
offluoride(F )ions 243
Contents ix
8.2 Rareearthmetal-organicframeworkhybridmaterials
forluminescenceresponsivechemicalsensingofother
simpleanions(S22,HS2,andSCN2) 246
8.3 Rareearthmetal-organicframeworkhybridmaterialsfor
luminescenceresponsivechemicalsensingofmaingroup
elementoxysaltanions 252
8.4 Rareearthmetal-organicframeworkhybridmaterialsfor
luminescenceresponsivechemicalsensingoftransition
metaloxysaltsanions 262
References 272
Part IV
Rare earth metal-organic frameworks hybrid
materials as luminescence response chemical
sensors for typical molecular analytes
9. Rare earth metal-organic framework hybrid materials
for luminescence responsive chemical sensing of
general molecules
9.1 Rareearthmetal-organicframeworkhybridmaterialsfor
luminescenceresponsivechemicalsensingofinorganic
molecules 284
9.2 Rareearthmetal-organicframeworkforluminescence
responsivechemicalsensingofgeneralorganic
molecules 300
9.3 Rareearthmetal-organicframeworkhybridmaterials
forluminescenceresponsivechemicalsensingofgeneral
organicpollutantmolecules 312
References 317
10. Rare earth metal-organic framework hybrid materials
for luminescence responsive chemical sensing of
special molecule species
10.1 Rareearthmetal-organicframeworkhybridmaterials
forluminescenceresponsivechemicalsensing
ofbiomolecularspecies 327
10.2 Rareearthmetal-organicframeworkhybridmaterials
forluminescenceresponsivechemicalsensing
ofantibioticsanddrugs 340
10.3 Rareearthmetal-organicframeworkhybridmaterials
forluminescencesensingofnitroaromaticexplosives(NAE)
andotherspecialdangerousspecies 353
References 365
