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“Multiporphyrin Arrays brings together in one comprehensive collection articles from top researchers whose combined contributions serve to introduce and define the field of multiporphyrin arrays — systems built up through the covalent and non-covalent linking of multiple porphyrin chromophores — and detail its importance in terms of topic areas running the gamut from the M edited by Dongho Kim very fundamental to the fully applied. The book thus provides a tutorial on how detailed research endeavors can lead to practical payoffs with real-world utility.” Prof. Jonathan Sessler u The University of Texas at Austin, USA Multipor phyrin l “Each chapter includes a good introduction and the contents are well organized. This book serves t as a first-rate resource for graduate students or anyone who is new to the fields of porphyrins and photophysics and their applications.” i Prof. Shunichi Fukuzumi p Arrays Osaka University, Japan “Multiporphyrin Arrays brings together some of the top scientists in the field to yield a timely, o coherent, and thorough summary of the current state of the art of these extraordinary functional materials. This book should be a valuable resource for all those who are interested in porphyrinic r materials and molecular photonics.” Fundamentals Prof. Charles Michael Drain p Hunter College of the City University of New York, USA and Applications h Porphyrins are very attractive constituent elements for molecule-based devices because of their excellent electronic and photonic properties and their amenability to synthetic modification to afford well-defined elaborate structures. Porphyrin molecules must be organized into well-defined architectures by means of y directional intermolecular interactions, covalent or noncovalent, for cooperative performances. This book provides a comprehensive review of the fundamentals and applications of multiporphyrin arrays ranging r from basic spectroscopic features to a wide range of promising applications such as molecular wires, switches, sensors, artificial photosynthetic devices, and dye-sensitized solar cells based on a variety of i multiporphyrin architectures using covalent or noncovalent molecular assemblies. Particularly, it focuses on n energy and electron transfer processes occurring in multiporphyrin arrays in various environments such as single-molecule level, composite materials, LB films, and solid surface to provide a better understanding of photofunctional molecular architectures. A Dongho Kim received his BS in 1980 from Seoul National University, Seoul, South Korea, and PhD in 1984 from Washington University, Washington, DC. After postdoctoral research at Princeton University, New Jersey, he joined the Korea r Research Institute of Standards and Science, Daejeon, South Korea, in 1986. r In 2000, he moved to Yonsei University, Seoul, South Korea, as a professor of chemistry. He has received several awards, including the Sigma-Aldrich Award a (2005) and the Korea Science Award in Chemistry (2006). Since 2002, Dr. Kim has been a fellow of the Korea Academy of Science and Technology. Currently, he y leads the Center for Smart Nano-Conjugates through the World Class University Program. His research activity is focused on the experimental investigation of pi- s conjugated molecular systems such as porphyrin, pyrene, perylenebisimide, and thiophene and their assemblies, with particular interest in excitation dynamics both in ensemble and at the single-molecule level. He has coauthored more than 350 articles and about 15 reviews in journals and books. Kim V266 ISBN-13 978-981-4316-60-6 Multipor_TP.indd 2 11/29/11 5:55:03 PM TThhiiss ppaaggee iinntteennttiioonnaallllyy lleefftt bbllaannkk Multipor_TP.indd 1 11/29/11 5:55:02 PM CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2012 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Version Date: 20120113 International Standard Book Number-13: 978-9-81436-428-7 (eBook - PDF) This book contains information obtained from authentic and highly regarded sources. Reason- able efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use. The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint. Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. 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Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com December1,2011 12:57 PSPBook-9inx6in 00-Dongho–prelims Contents Preface xvii 1 Single-MoleculePhotophysicalPropertiesofVarious DirectlyLinkedPorphyrinArrays 1 DonghoKimandAtsuhiroOsuka 1.1 Introduction 1 1.2 DirectlyMeso-MesoLinkedLinearPorphyrinArrays 3 1.2.1 ExcitonCouplinginZ 4 N 1.2.1.1 ElectronicnatureofexcitonsplitSoret band 4 1.2.1.2 PhotobleachingdynamicsofZ2 provesexcitoncoupling 5 1.2.2 PhotobleachingDynamicsofZ 6 N 1.2.3 ExcitonCoherenceLengthofZ 9 N 1.2.3.1 Excitoncoherencelengthatthe ensemblelevel 9 1.2.3.2 Excitoncoherencelengthatthe single-moleculelevel 11 1.2.4 ConformationalHeterogeneitiesinZ 12 N 1.2.4.1 Conformationalheterogeneitiesatthe ensemblelevel 12 1.2.4.2 Conformationalheterogeneitiesatthe single-moleculelevel 15 1.3 Butadiyne-LinkedLinearPorphyrinArrays 16 1.3.1 Controlofexcited-stateconformational dynamicsofZ2B 16 1.3.2 PhotobleachingdynamicsofZ B:one N quantumsystem 20 1.3.3 Wannier-MottexcitonsinZ Bpromote N fluorescenceintermittency 24 December1,2011 12:57 PSPBook-9inx6in 00-Dongho–prelims vi Contents 1.4 FusedLinearPorphyrinArrays 25 1.4.1 EnergyRelaxationDynamicsinTB 26 N 1.5 CyclicPorphyrinWheels 29 1.5.1 ExcitonCouplinginC ZA 29 N 1.5.1.1 ExcitoncouplinginZ2,2Z2,and C12ZA 29 1.5.1.2 Excitoncouplinginlargercyclic porphyrinwheels 31 1.5.2 Single-MoleculeFluorescenceDynamics ofC12ZA 32 1.5.3 ExcitationEnergyTransferinC ZA 34 N 1.5.3.1 Rateofexcitationenergyhoppingin C12ZA 34 1.5.3.2 Efficienciesofexcitationenergy transferatthesinge-moleculelevel 38 1.5.4 ConformationalHeterogeneitiesinC ZA 40 N 1.5.4.1 Conformationalheterogeneitiesat theensemblelevel 40 1.5.4.2 Conformationalheterogeneitiesat thesingle-moleculelevel 42 1.6 ConclusionsandFutureOutlook 44 2 ElectronTransferThroughButadiyne-Linked Porphyrin-BasedMolecularWires 55 BoAlbinssonandHarryL.Anderson 2.1 Introduction 55 2.2 MolecularDesign 58 2.3 ElectronicStatesandSpectraofButadiyne-Linked PorphyrinArrays 60 2.4 ComputationalModeling 64 2.5 ConformationalControlofChargeSeparationand RecombinationinButadiyne-LinkedPorphyrins 71 2.6 Long-RangeElectronTransferMediatedby PorphyrinOligomers 76 2.7 DiscussionofElectron-TransferRates 80 2.7.1 Tunneling 80 2.7.2 Hopping 82 2.7.3 RecombinationviaTripletStates 83 December1,2011 12:57 PSPBook-9inx6in 00-Dongho–prelims Contents vii 2.8 ConclusionsandOutlook 83 2.9 NoteAddedinProof 84 3 RecentApplicationsofMCDSpectroscopyto Porphyrinoids 91 JohnMackandNagaoKobayashi 3.1 Introduction 92 3.1.1 FaradayTerms 94 3.1.2 Gouterman’s4-OrbitalModel 96 3.1.3 Michl’s(4N+2)-Electronand4N-Perimeter Models 98 3.1.4 TD-DFTCalculationsofUV-VisibleAbsorption Spectra 104 3.1.5 TD-DFTCalculationsofMCDSpectra 108 3.2 RadiallySymmetricPorphyrinoids 109 3.2.1 Non-PlanarPorphyrinoids 110 3.2.2 Ring-ContractedPorphyrinoids 113 3.2.3 Ring-ExpandedPorphyrinoids 116 3.3 Low-SymmetryPorphyrinoids 117 3.3.1 Core-ModifiedTetrabenzoprophyrins 118 3.3.2 Triphyrins 122 3.3.3 Corrolazines 124 3.3.4 Tetraazachlorins 126 3.3.5 PartiallyBenzo-FusedPorphyrazinesand Phthalocyanines 127 3.3.6 Azulene-FusedPorphyrinsand Azulenocyanines 128 3.3.7 Benzoporphycenes 129 3.4 TransitionMetalPorphyrinoids 131 3.5 Conclusions 135 4 Phthalocyanine–PorphyrinHeteroarrays:APerfect MarriageBetweenTwoUniqueMacrocycles 149 GiovanniBottari,GemadelaTorre,DirkM.Guldi andTomasTorres, 4.1 Introduction 149 4.2 CovalentlyLinked,Phthalocyanine–Porphyrin Heteroarrays 151 December1,2011 12:57 PSPBook-9inx6in 00-Dongho–prelims viii Contents 4.2.1 Peripherallylinked,Phthalocyanine–Porphyrin Heteroarrays 151 4.2.2 AxiallyBonded,Phthalocyanine–Porphyrin Heteroarrays 167 4.3 SupramolecularPhthalocyanine–Porphyrin Heteroarrays 171 4.4 PhthalocyaninesandPorphyrinsonMetalSurfaces 191 4.5 Phthalocyanine-Subphthalocyanineand Porphyrin-SubphthalocyanineHeteroarrays 194 4.6 Donor–AcceptorMultiporphyrinoidHomo-and Heteroarrays 198 4.6.1 CovalentlyLinkedEnsembles 198 4.6.2 SystemsAssembledviaSupramolecular Interactions 207 5 PrimaryPhotoeventsinSelf-AssembledComplexes: MultiporphyrinArraysand“SemiconductorCdSe/ZnS Nanocrystal-Porphyrin”Composites 217 EduardZenkevichandChristianvonBorczyskowski 5.1 Introduction 218 5.1.1 PhotosyntheticAspectsandApplicationsin Nanotechnology 218 5.1.2 SyntheticApproachesintheFormationof MultiporphyrinArraysand“Semiconductor NC-Porphyrin”Nanocomposites 222 5.1.2.1 Self-assembledcomplexeswith participationoftetrapyrrole molecules 223 5.1.2.2 Self-assembledinorganic–organic nanocompositescontaining semiconductorCdSe/ZnS nanocrystalsandporphyrins 227 5.2 ExcitedStatesRelaxationandEnergyTransferin PorphyrinChemicalDimers 229 5.2.1 InterchromophoricInteractionsandEnergy Transferin–CH -CH –BridgedDimers 230 2 2 5.2.2 EnergyTransferinChemicalDimersof Cyclopentaneporphyrins 237 December1,2011 12:57 PSPBook-9inx6in 00-Dongho–prelims Contents ix 5.2.3 StericHindranceEffectsandExcitedState RelaxationinPhenyl-BridgedDimers 239 5.3 CompetitionBetweenEnergyandPhotoinduced ElectronTransferProcessesinSelf-Assembled PorphyrinTriads 241 5.3.1 Steady-StateandTime-ResolvedData 242 5.3.2 MechanismsandPathwaysofRelaxation Dynamics 245 5.3.3 UltrafastPETinTriadContainingFluorinated Extra-Ligand 248 5.4 TriadswithCovalentlyLinkedElectronAcceptorsof Non-PorphyrinNature 250 5.4.1 PhotoinducedPETinDimersCovalently LinkedtoElectronAcceptors 251 5.4.2 SuperexchangeElectronTransferinTriads withCovalentlyLinkedElectronAcceptors 253 5.5 ExcitedStatePropertiesofMultiporphyrinComplexes withNumberofMacrocyclesN ≥5 258 5.5.1 Exchanged-π EffectsinSelf-Assembled ComplexesContainingCu-Porphyrins 259 5.5.2 RelaxationPathwaysinMulticomponent Complexes 263 5.6 ExcitonRelaxationandElectronWaveTunnelingin Self-Assembled“Semiconductor Nanocrystal–Porphyrin”Composites 266 5.7 Conclusions 272 6. StructuralandFunctionalMimicsofLight-Harvesting SystemsinBacterialPhotosynthesis 289 YoshiakiKobuke 6.1 Introduction 289 6.2 ChromophoreArrangementsinthePhotosynthetic System 291 6.3 MethodologyforPhotosyntheticMimics 295 6.4 Light-HarvestingAntennaRing 299 6.5 LinearAntennaArray 312 6.6 IntraringExcitedEnergyTransfer 318 6.7 Antenna–ReactionCenterComposite 322