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Supramolecular Coordination Complexes Supramolecular Coordination Complexes Design, Synthesis, and Applications Editedby Sankarasekaran Shanmugaraju DepartmentofChemistry,IndianInstituteofTechnologyPalakkad (IITPKD),Palakkad,Kerala,India Elsevier Radarweg29,POBox211,1000AEAmsterdam,Netherlands TheBoulevard,LangfordLane,Kidlington,OxfordOX51GB,UnitedKingdom 50HampshireStreet,5thFloor,Cambridge,MA02139,UnitedStates Copyright©2023ElsevierInc.Allrightsreserved. Nopartofthispublicationmaybereproducedortransmittedinanyformorbyanymeans, electronicormechanical,includingphotocopying,recording,oranyinformationstorage andretrievalsystem,withoutpermissioninwritingfromthepublisher.Detailsonhowto seekpermission,furtherinformationaboutthePublisher’spermissionspoliciesandour arrangementswithorganizationssuchastheCopyrightClearanceCenterandtheCopy- rightLicensingAgency,canbefoundatourwebsite:www.elsevier.com/permissions. Thisbookandtheindividualcontributionscontainedinitareprotectedundercopyright bythePublisher(otherthanasmaybenotedherein). Notices Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices,ormedicaltreatmentmaybecomenecessary. Practitionersandresearchersmustalwaysrelyontheirownexperienceandknowledgein evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility. To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matterofproductsliability,negligenceorotherwise,orfromanyuseoroperationofany methods,products,instructions,orideascontainedinthematerialherein. ISBN:978-0-323-90582-4 ForInformationonallElsevierpublicationsvisitourwebsiteat https://www.elsevier.com/books-and-journals Publisher:SusanDennis AcquisitionsEditor:CharlesBath EditorialProjectManager:KyleGravel ProductionProjectManager:RashmiManoharan CoverDesigner:GregHarris TypesetbyAptara,NewDelhi,India 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

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