Table Of ContentVincenzo Balzani, Alberto Credi,
and Margherita Venturi
Molecular Devices and Machines
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Vincenzo Balzani, Alberto Credi,
and Margherita Venturi
Molecular Devices and Machines
Concepts and Perspectives for the Nanoworld
Second Edition
TheAuthors AllbookspublishedbyWiley-VCHarecarefully
produced.Nevertheless,authors,editors,and
Prof.VincenzoBalzani publisherdonotwarranttheinformationcontained
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errors.Readersareadvisedtokeepinmindthat
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040126Bologna
Italy #2008WILEY-VCHVerlagGmbH&Co.KGaA,
Weinheim
Cover
LeonardodaVinci:“Two-wheelhoist” Allrightsreserved(includingthoseoftranslationinto
CodexAtlanticus(BAM),fol.30v otherlanguages).Nopartofthisbookmaybe
©IstitutoeMuseodiStoriadellaScienza reproducedinanyform–byphotoprinting,
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RotaxaneMolecule(AlbertoCredi) permissionfromthepublishers.Registerednames,
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unprotectedbylaw.
Composition ThomsonDigital,Noida,India
Printing StraussGmbH,Mörlenbach
Bookbinding Litges&DopfGmbH,Heppenheim
CoverDesign AdamDesign,Weinheim
PrintedintheFederalRepublicofGermany
Printedonacid-freepaper
ISBN:978-3-527-31800-1
V
Contents
Preface to the Second Edition XV
Glossary XVII
List of Abbreviations XXXIII
I GeneralConcepts 1
1 Introduction 3
1.1 DevicesandMachinesattheMolecularLevel 3
1.2 NanoscienceandNanotechnology 5
1.3 Supramolecular(Multicomponent)Chemistry 7
1.4 Top-Down(Large-Downward)Approach 10
1.5 Bottom-Up(Small-Upward)Approach 10
1.6 Bottom-upMolecule-by-MoleculeApproach 11
1.7 Self-OrganizationandCovalentSyntheticDesign 13
1.8 EnergyandSignals 15
2 ProcessingEnergyandSignalsbyMolecularandSupramolecular
Systems 23
2.1 Introduction 23
2.2 MolecularElectronics 25
2.3 MolecularPhotonics 27
2.4 MolecularChemionics 28
2.5 MolecularElectrophotonics 29
2.5.1 SolutionSystems 30
2.5.2 SolidState 31
2.6 MolecularElectrochemionics 31
2.7 MolecularPhotoelectronics 33
2.7.1 PhotoinducedElectronTransferinHomogeneousSystems 33
2.7.2 PhotoinducedPotentialGenerationinHeterogeneousSystems 33
2.8 MolecularPhotochemionics 34
2.8.1 ProtonReleaseorUptake 35
MolecularDevicesandMachines.ConceptsandPerspectivesfortheNanoworld.2ndEd.
VincenzoBalzani,AlbertoCredi,andMargheritaVenturi
Copyright(cid:1)2008WILEY-VCHVerlagGmbH&Co.KGaA,Weinheim
ISBN:978-3-527-31800-1
VI Contents
2.8.2 MetalIonRelease 35
2.8.3 AnionRelease 36
2.8.4 MoleculeRelease 36
2.8.5 ConfigurationalChanges 37
2.9 MolecularChemiophotonics 38
2.10 MolecularChemioelectronics 38
2.11 MultipleInput/Processes 39
2.11.1 ASequenceofTwoChemicalandaPhotonicInputs
GeneratingPhotonEmission 39
2.11.2 TwoElectrochemicalInputsinParallelGeneratinga
ChemicalandaPhotonicProcessinaSequence 39
2.11.3 APhotonicInputGeneratingParallelandSerialProcesses 40
II MolecularDevicesforProcessingElectronsand
ElectronicEnergy 47
3 FundamentalPrinciplesofPhotoinducedElectronand
EnergyTransfer 49
3.1 MolecularandSupramolecularPhotochemistry 49
3.1.1 MolecularPhotochemistry 49
3.1.2 SupramolecularPhotochemistry 51
3.2 ElectronTransfer 53
3.2.1 MarcusTheory 53
3.2.2 QuantumMechanicalTheory 56
3.2.2.1 TheElectronicFactor 56
3.2.2.2 TheNuclearFactor 58
3.2.2.3 OpticalElectronTransfer 59
3.3 EnergyTransfer 60
3.3.1 CoulombicMechanism 61
3.3.2 ExchangeMechanism 62
3.4 RoleoftheBridge 63
4 WiresandRelatedSystems 69
4.1 Introduction 69
4.2 ConductivityMeasurements 69
4.3 Electron-TransferProcessesatElectrodes 72
4.4 Wire-TypeSystemsBasedonPhotoinducedChargeSeparation 73
4.4.1 Introduction 73
4.4.2 Dyads,Triads,andLargerSystems 73
4.4.3 CovalentlyLinkedSystemsContainingMetalComplexes 75
4.4.4 CovalentlyLinkedSystemsContainingPorphyrins 79
4.4.5 CovalentlyLinkedSystemsBasedonOrganicCompounds 83
4.4.6 DNAandRelatedSystems 86
4.5 HeterogeneousPhotoinducedElectronTransfer 88
Contents VII
4.6 EnergyTransfer 89
4.6.1 CovalentlyLinkedSystemsContainingMetalComplexes 89
4.6.2 CovalentlyLinkedSystemsContainingPorphyrins 93
4.6.3 CovalentlyLinkedSystemsBasedonOrganicCompounds 95
4.6.4 DNAandRelatedSystems 97
5 SwitchingElectron-andEnergy-transferProcesses 107
5.1 Introduction 107
5.2 SwitchingofElectron-TransferProcesses 108
5.2.1 PhotonInputs 108
5.2.1.1 Long-LivedSwitching 109
5.2.1.2 FastandUltrafastSwitching 112
5.2.2 RedoxInputs 116
5.2.3 Acid–BaseInputs 117
5.2.4 OtherFactors 121
5.3 SwitchingofEnergy-TransferProcesses 122
5.3.1 PhotonInputs 122
5.3.2 RedoxInputs 125
5.3.3 Acid–BaseInputs 125
5.3.4 OtherFactors 127
6 LightHarvestingAntennae 135
6.1 Introduction 135
6.2 NaturalAntennaSystems 136
6.3 Dendrimers 138
6.3.1 Porphyrin-BasedArraysandDendrimers 139
6.3.1.1 Arrays 139
6.3.1.2 Dendrimers 143
6.3.2 DendrimersContainingMetalComplexes 145
6.3.2.1 MetalComplexesasCores 145
6.3.2.2 MetalComplexesinEachBranchingCenter 147
6.3.3 DendrimersBasedonOrganicChromophores 150
6.3.3.1 Poly(arylether)Dendrimers 150
6.3.3.2 PhenylacetyleneDendrons 150
6.3.3.3 PolyphenyleneandOligo(p-PhenyleneVinylene)Dendrimers 152
6.3.4 Host–GuestSystems 153
6.3.4.1 HostingOrganicMolecules 153
6.3.4.2 HostingMetalIons 156
6.4 OtherSystems 159
6.4.1 MultichromophoricCyclodextrins 160
6.4.2 Phthalocyanines 160
6.4.3 MetallosupramolecularSquares 160
6.4.4 Rotaxanes 161
6.4.5 Zeolites 162
6.4.6 Polyelectrolytes 162
VIII Contents
6.4.7 Polymers 162
6.4.8 Self-AssemblyofBiologicalStructures 164
7 SolarEnergyConversion 171
7.1 Introduction 171
7.2 NaturalPhotosynthesis 173
7.2.1 Introduction 173
7.2.2 BacterialPhotosynthesis 174
7.2.3 PhotosystemII 177
7.3 ArtificialPhotosynthesis 179
7.3.1 Introduction 179
7.3.2 HydrogenEconomy 179
7.3.3 PhotochemicalWaterSplitting 180
7.3.4 CouplingArtificialAntennasandReaction-CenterBuilding
Blocks 182
7.3.4.1 Introduction 182
7.3.4.2 SystemsBasedonOrganicCompoundsandPorphyrins 183
7.3.4.3 SystemsBasedonMetalComplexes 188
7.3.5 CouplingSingle-PhotonCharge-SeparationwithMulti-Electron
RedoxProcesses 189
7.3.5.1 Introduction 189
7.3.5.2 CouplingElectronandProtonTransferforOxygenEvolution 190
7.3.5.3 OtherSystems 193
7.3.6 AssemblyStrategies 193
7.3.6.1 Introduction 193
7.3.6.2 Self-Assembly 193
7.3.6.3 BilayerMembranes 195
7.4 HybridSystems 195
7.4.1 HybridPhotosyntheticReactionCenter 195
7.4.2 ConversionofLighttoaProton-MotiveForce 196
7.4.3 Light-DrivenProductionofATP 198
7.5 ConversionofLightintoElectricitybyPhotoelectrochemicalCells 199
III Memories,LogicGates,andRelatedSystems 209
8 BistableandMultistableSystems 211
8.1 Introduction 211
8.2 EnergyStimulation 212
8.2.1 StimulationbyPhotons:PhotochromicSystems 213
8.2.2 StimulationbyElectrons:ElectrochromicSystems 216
8.3 BistableSystems 217
8.3.1 ModulationofHost–GuestInteractions 217
8.3.2 FluorescentSwitches 218
8.3.3 ChiropticalSwitches 219
Contents IX
8.3.4 PhotochemicalBiomolecularSwitches 222
8.3.5 RedoxSwitches 223
8.3.6 OtherSystems 224
8.4 MultistableSystems 225
8.4.1 Bi-andMultiphotochromicSupramolecularSystems 225
8.4.2 PhotochemicalInputsCoupledwithotherStimuli 226
8.4.2.1 Three-StateSystems:Write–Lock–Read–Unlock–EraseCycles 227
8.4.2.2 OrtogonalPhotochemical–ElectrochemicalStimulations 230
8.4.2.3 OrtogonalPhotochemical–(Acid–Base)Stimulations 233
8.4.3 MultielectronRedoxProcesses 236
8.4.3.1 SystemswithEquivalentRedoxUnits 238
8.4.3.2 SystemswithNonequivalentRedoxUnits 242
8.4.4 ElectrochemicalInputsCoupledwithChemicalInputs 245
8.4.5 MultipleChemicalInputs 246
9 LogicGatesandCircuits 259
9.1 Introduction 259
9.1.1 InformationProcessingBasedonElectronics 259
9.1.2 BiologicalInformationProcessing 260
9.1.3 TheChemicalComputer 260
9.2 FundamentalConceptsofLogicGates 261
9.3 MolecularSwitchesasLogicGates 263
9.3.1 Input/OutputSignals 263
9.3.2 Reconfiguration,Superposition,andIntegration 265
9.4 BasicLogicGates 266
9.4.1 YESandNOTGates 266
9.4.2 ORandNORGates 267
9.4.3 ANDandNANDGates 269
9.4.4 XORandXNORGates 272
9.4.5 INHGate 273
9.5 CombinationalLogicCircuits 274
9.5.1 EnORandEnNORFunctions 275
9.5.2 OtherFunctions 276
9.5.3 SignalCommunicationBetweenMolecularSwitches 277
9.5.4 Half-AdderandHalf-Subtractor 279
9.5.5 Full-AdderandFull-Subtractor 283
9.5.6 AMolecular2-to-1DigitalMultiplexer 287
9.6 SequentialLogicCircuits 288
9.6.1 MolecularMemories 289
9.6.2 AMolecularKeypadLock 290
9.7 Neural-TypeSystems 293
9.7.1 ALogicDeviceunderControlofanIntrinsicThresholdMechanism 293
9.7.2 APerceptron-TypeScheme 295
9.8 LogicDevicesBasedonBiomolecules 296
9.9 HeterogeneousSystems 299
X Contents
9.10 ApplicationsofMolecularLogic 300
9.11 Conclusions 303
IV Molecular-ScaleMechanicalDevices,Machines,andMotors 313
10 BasicPrinciples 315
10.1 Introduction 315
10.2 BiomolecularMachinesandtheBrownianMotion 316
10.3 ArtificialSystems 317
10.3.1 TermsandDefinitions 319
10.3.2 MechanicalDevices 320
10.3.3 Machines 321
10.3.4 Motors 322
10.4 EnergySupply 322
10.4.1 ChemicalEnergy 323
10.4.2 LightEnergy 324
10.4.3 ElectricalEnergy 325
10.5 OtherFeatures 325
10.5.1 Motions 325
10.5.2 ControlandMonitoring 326
10.5.3 Reset 326
10.5.4 Timescale 326
10.5.5 Functions 327
11 SpontaneousMechanical-LikeMotions 331
11.1 Introduction 331
11.2 Rotors 331
11.3 Cogwheels 332
11.4 Gears 333
11.5 PaddleWheels 335
11.6 Turnstiles 335
11.7 Brakes 337
11.8 Ratchets 338
11.9 GyroscopesandCompasses 338
11.10 OtherMotions 340
12 MovementsRelatedtoOpening,Closing,andTranslocation
Functions 343
12.1 Introduction 343
12.2 AllostericMovements 343
12.2.1 AllostericEnzymes 343
12.2.2 ArtificialAllostericSystems 344
12.3 TweezersandHarpoons 346
12.3.1 Tweezers 346
