Table Of ContentSupramolecular
Coordination
Complexes
Supramolecular
Coordination
Complexes
Design, Synthesis, and Applications
Editedby
Sankarasekaran Shanmugaraju
DepartmentofChemistry,IndianInstituteofTechnologyPalakkad
(IITPKD),Palakkad,Kerala,India
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Contents
Contributors xiii
1. Supramolecularcoordinationself-assembly—
Ageneralintroduction 1
BindujaMohanandSankarasekaranShanmugaraju
1.1 Introduction 1
1.2 Coordination-drivenmolecularself-assembly 2
1.3 Backgroundanddesignprinciples 2
1.3.1 Directionalbondingapproach 4
1.3.2 Symmetryinteractionapproach 4
1.3.3 Panelingapproach 4
1.3.4 Weak-linkapproach 6
1.3.5 Dimetallicbuildingblockapproach 8
1.4 Characterizationofsupramolecularcoordinationcomplexes 8
1.5 Functionalizationofsupramolecularcoordinationcomplexes 11
1.6 Self-sortingandself-selectioninsupramolecularcoordination
complexformation 14
1.7 Selectedexamplesof2Dand3Dsupramolecularcoordination
complexes 16
1.8 Conclusion 21
Acknowledgment 21
References 21
2. Supramolecularcoordinationcomplexesfrom
metalloligands:Hydrogenbonding-based
self-assemblies 25
RuchikaGupta,SanyaPachisiaandRajeevGupta
2.1 Introduction 25
2.2 Coordinationcomplexesasthemetalloligandscontaining
appendedH-bondingfunctionalgroups 26
2.3 Synthesisandcharacterizationofmetalloligands 27
2.4 Metalloligandsofferingdifferentappendedfunctionalgroups 30
2.4.1 Metalloligandsofferingappendedphenolandcatechol
groups 30
2.4.2 Metalloligandsofferingappendedarylcarboxylicacid
groups 35
v
vi Contents
2.5 Conclusions 39
Acknowledgments 40
References 40
3. Supramolecularcoordinationcomplexesfrom
metalloligands:Heteronuclearcomplexesand
coordinationpolymersandtheirapplications
incatalysis 43
RuchikaGupta,SanyaPachisiaandRajeevGupta
3.1 Introduction 43
3.2 Synthesisandcharacterizationofmetalloligands 44
3.3 Metalloligandsofferingdifferentappendedfunctionalgroups 48
3.3.1 Metalloligandsofferingappendedpyridylrings 44
3.3.2 Metalloligandsofferingotherappendedheterocyclicrings 52
3.3.3 Metalloligandsofferingappendedarylcarboxylicacid
groups 56
3.4 Catalyticaspects 59
3.4.1 Oxidationanddealkylationreactionsofsubstituted
phenols 60
3.4.2 A3-couplingreactions 60
3.4.3 Streckerreactions 61
3.4.4 Ring-openingreactions(RORs) 62
3.4.5 Knoevenagelcondensationreactions 62
3.5 Conclusions 63
Acknowledgments 64
References 64
4. Platinum-containingheterometallicmetallacyclesand
metallacages 69
Hong-YuLin,Yu-TeWang,DaweiZhangandLinXu
4.1 Introduction 69
4.2 Platinum-containingheterometallicmetallacycles 70
4.2.1 Pt–Pdheterometallicmetallacycles 70
4.2.2 Pt–Znheterometallicmetallacycles 72
4.2.3 Pt–Feheterometallicmetallacycles 74
4.2.4 Pt–Cuheterometallicmetallacycles 79
4.2.5 Pt–Irheterometallicmetallacycles 81
4.2.6 Pt–Lnheterometallicmetallacycles 81
4.3 Platinum-containingheterometallicmetallacages 83
4.3.1 Pt–Al/Gaheterometallicmetallacages 83
4.3.2 Pt–Ruheterometallicmetallacages 84
4.3.3 Pt–Znheterometallicmetallacages 85
4.3.4 Pt–Feheterometallicmetallacages 86
4.3.5 Pt–Coheterometallicmetallacages 90
4.3.6 Pt–Pdheterometallicmetallacages 93
Contents vii
4.4 Conclusionandperspective 94
References 96
5. Self-assemblyofpyrazine-basedmetallamacrocycles:
Design,synthesis,andapplications 101
SaurabhKumarandNeeladriDas
5.1 Introduction 101
5.2 Moleculartriangles 103
5.3 Molecularsquares 106
5.4 Molecularrectangles 108
5.5 Molecularhexagons 111
5.5.1 Ionichexagonalmacrocycles 112
5.5.2 Neutralhexagonalmacrocycles 122
5.6 Ringsandcages 125
5.7 Conclusionsandoutlook 127
Acknowledgments 129
References 129
6. Rhenium(I)-basedsupramolecularcoordination
complexes:Synthesisandfunctionalproperties 133
K.R.Soumya,IshaMishra,MoonKedia,UpasanaPhukon,
ReemaBorkarandMalaichamySathiyendiran
6.1 Introduction 133
6.2 Metalprecursorsforsupramoleculararchitectures 134
6.3 Organicligandsassourcesforanionicbuildingframeworks 135
6.4 FlexiblebidentateN,Ndonorswithether,ester,oramide
functionalitiesanditsSCCs 136
6.5 Neutralrigidpyridine-basedditopic-andtritopic
ligandsanditsSCCs 137
6.6 NeutralflexibleditopicP=OdonorligandsanditsSCCs 140
6.7 NeutralflexibletritopicN-donorligandsanditsSCCs 141
6.8 NeutralflexibletetratopicN-donorligandsanditsSCCs 143
6.9 NeutralflexiblehexatopicN-donorligandsanditsSCCs 144
6.10 Neutralflexiblebenzimidazole-basedditopicN-donor
ligandsanditsSCCs 145
6.11 Heteroatomdonor-basedligandsanditsSCCs 149
6.12 Applicationsoffac-Re(CO) core-basedSCCs 150
3
References 153
7. Photoswitchingself-assembledcoordination
macrocycles:Synthesisandfunctionalapplications 159
AniketChowdhury
7.1 Introduction 159
7.2 Bisthienylethenebuildingblock-basedSCC 160
viii Contents
7.3 Styrylbuildingblock-basedSCC 172
7.4 Azobuildingblock-basedSCC 173
7.5 Spiropyranbuildingblocks-basedSCC 177
7.6 Host–guestinteractiondrivenphotochromisminSCC 180
7.7 Conclusion 188
Acknowledgment 189
References 189
8. Photoactivefinitesupramolecularcoordinationcages
forphotodynamictherapy 191
NidhiTyagiandPrakashP.Neelakandan
8.1 Introduction 191
8.2 SCCsforPDTapplications 194
8.2.1 SCCscontainingporphyrins 195
8.2.2 SCCscontainingBODIPYs 199
8.2.3 SCCscontainingrutheniumcomplexes 203
8.2.4 OthersSCCs 206
8.3 Conclusionandfutureprospects 209
Acknowledgment 210
References 210
9. Biosensingpropertiesofsupramolecular
coordinationcomplexes 215
DipanjanaSarkar,PanduranganNanjanand
SankarasekaranShanmugaraju
9.1 Introduction 215
9.2 Biosensingpropertiesofsupramolecular
coordinationcomplexes(SCCs) 216
9.2.1 InteractionofSCCswithnucleosides 216
9.2.2 InteractionofSCCswithnucleicacids 218
9.2.3 InteractionofSCCswithproteinandaminoacids 220
9.2.4 InteractionofSCCswithcarbohydrates 224
9.2.5 InteractionofSCCswithsteroidsandfattyacids 228
9.3 Conclusion 231
Acknowledgments 231
References 231
10. Hierarchicalmolecularself-assembliesof
coordinationcomplexes 235
KrishnanKarthaKalathilandGustavoFernández
10.1 Introduction 235
10.2 Hierarchicalself-assemblyofmetalcomplexes
containingπ-systems 236
10.3 Effectofhydrogenbondingontheself-assembly
ofmetalcomplexesinsolution 243
Contents ix
10.4 Hierarchicalself-assemblyofmetalcomplexesin
solutiondrivenbyhydrophobicinteractions 249
10.5 Hierarchicalself-assemblyofmetalcomplexesthrough
host–guestinteractions 252
10.6 Conclusion 257
References 258
11. Biomimeticsupramolecularcoordinationchemistry
andmolecularmachines 265
RenittaBenny,DiptipravaSahoo,NithishKumarKS
andSoumenDe
11.1 Introduction 265
11.2 Redox-triggeredmolecularmotion 266
11.3 Exchangeofmetalions 270
11.3.1 Additionandremovalofmetalions 272
11.4 Applicationofmolecularmotion 276
11.4.1 Chiralityinversion 276
11.4.2 Guestreleaseanduptake 279
11.4.3 Switchablecatalysis 283
11.4.4 Signaltransductionandnetworkingof
severalswitches 287
11.5 Conclusionandoutlook 290
References 291
12. Biomedicalapplicationofsupramolecular
coordinationcomplexes 299
SushobhanGhosh
12.1 Introduction 299
12.2 Platinumcomplexesasanticanceragent 300
12.3 Palladiumcomplexesasanticanceragent 314
12.4 Rutheniumandothermetallosupramolecularcomplexes
asanticanceragent 321
References 324
13. Riseofsupramolecularnanozymes:Next-generation
peroxidaseenzyme-mimeticmaterials 329
HuidromMangalsana,AbhijeetMohantyandAmitA.Vernekar
13.1 Introduction 329
13.1.1 Whatarenanozymes? 329
13.1.2 Whatissupramolecularchemistry? 330
13.1.3 Supramolecularnanozymes 331
13.2 Peroxidases 331
13.2.1 MOFsAsPeroxidasemimics 332
13.2.2 COFsasperoxidasemimics 364
13.2.3 NCsasperoxidasemimics 366
