Multiporphyrin arrays : fundamentals and applications

817 Pages·2012·25.883 MB·xix, 775, 32 p. : ill. ; 24 cm\817

by  Dongho Kim

“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
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Multipor_TP.indd 1 11/29/11 5:55:02 PM
CRC Press
Taylor & Francis Group
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© 2012 by Taylor & Francis Group, LLC
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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