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Electron Transfer
Electron Transfer

Mechanisms and Applications

Shunichi Fukuzumi
Author All books published by Wiley-VCH
are carefully produced. Nevertheless,
Shunichi Fukuzumi authors, editors, and publisher do not
Department of Material & Life Science warrant the information contained in
Osaka University these books, including this book, to
2-1 Yamada-oka, Suita be free of errors. Readers are advised
Osaka University to keep in mind that statements, data,
565-0871 Osaka illustrations, procedural details or other
Japan items may inadvertently be inaccurate.

Library of Congress Card No.:

applied for

British Library Cataloguing-in-Publication

Data
A catalogue record for this book is
available from the British Library.

Bibliographic information published by

the Deutsche Nationalbibliothek
The Deutsche Nationalbibliothek lists
this publication in the Deutsche
Nationalbibliografie; detailed
bibliographic data are available on the
Internet at <http://dnb.d-nb.de>.

© 2020 Wiley-VCH Verlag GmbH &

Co. KGaA, Boschstr. 12, 69469
Weinheim, Germany

All rights reserved (including those of

translation into other languages). No
part of this book may be reproduced in
any form – by photoprinting,
microfilm, or any other means – nor
transmitted or translated into a
machine language without written
permission from the publishers.
Registered names, trademarks, etc. used
in this book, even when not specifically
marked as such, are not to be
considered unprotected by law.

Print ISBN: 978-3-527-32666-2

ePDF ISBN: 978-3-527-65180-1
ePub ISBN: 978-3-527-65179-5
oBook ISBN: 978-3-527-65177-1

Typesetting SPi Global, Chennai, India

Printing and Binding

Printed on acid-free paper

10 9 8 7 6 5 4 3 2 1
 v

Contents

Acknowledgments vii

1 Introduction 1

2 Marcus Theory of Electron Transfer 5

3 Photosynthetic Reaction Center Models 7

4 Electron Donor–Acceptor Dyads 11

5 Supramolecular Electron Transfer 25

5.1 Cation–Anion Binding 25
5.2 π-Complexes 35
5.3 Electron-Transfer Switching 46
5.4 Dendrimers 53
5.5 Supramolecular Solar Cells 55

6 Effects of Metal Ions on Photoinduced Electron Transfer 65

7 Photoredox Catalysis 69
7.1 Photocatalytic Oxygenation 69
7.2 Photocatalytic Oxibromination 77
7.3 Carbon—Carbon Bond Formation 77
7.4 DNA Cleavage 81
7.5 Anti-Markovnikov Hydroetherification 81
7.6 Photocatalytic Cycloaddition 83
7.7 Photocatalytic Hydrotrifluoromethylation 85
7.8 Photocatalytic Hydrogen Evolution 86

8 Hydrogen Storage 93
8.1 Interconversion Between Hydrogen and Formic Acid 95
8.2 Interconversion Between Hydrogen and NADH 101
vi Contents

8.3 Hydrogen Evolution from Alcohols 104

8.4 Hydrogen Evolution from Paraformaldehyde 107

9 Metal Ion-Coupled Electron Transfer (MCET) 109

9.1 MCET of O2 109
9.2 Binding Modes of Metal Ions 114
9.3 Self-Organized MCET 124
9.4 Accelerating and Decelerating Effects of Metal Ions 132
9.5 Driving Force Dependence of MCET Rate Constants 137
9.6 MCET Coupled with Hydrogen Bonding 143
9.7 MCET Catalysis 148
9.7.1 Hydride Transfer vs. Cycloaddition 148
9.7.2 Suproxode Disumutase (SOD) Models 152
9.8 MCET of Metal-Oxo Complexes 157
9.9 PCET of Metal-Oxo Complexes 162
9.10 Unified Mechanism of MCET and PCET of Metal-Oxo
Complexes 165
9.11 MCET of Metal-Peroxo Complexes 169

10 Catalytic Reduction of O2 173

11 Catalytic Oxidation of H2 O 181

12 Production of Hydrogen Peroxide from Water and Oxygen as a

Solar Fuel 187

13 Production and Usage of Hydrogen Peroxide as a Solar Fuel in

Seawater 193

14 Photosystem II Mimic 197

15 Conclusion and Perspective 201

References 203

Index 225
 vii

Acknowledgments

The author gratefully acknowledges the contributions of his collaborators men-

tioned in the references. The author thanks Japan Science Technology Agency
and the Ministry of Education, Culture, Sports, Science and Technology of Japan
for the continuous support.
 1

Introduction

The rapid consumption of fossil fuel has already caused unacceptable

environmental problems such as the greenhouse effect by CO2 emission,
which is predicted to lead to disastrous climatic consequences [1]. Moreover, the
consumption rate of fossil fuels is expected to increase further at least twofold
relative to the present by midcentury because of population and economic
growth, particularly in the developing countries. It is becoming more and more
obvious that fossil fuels will run out eventually in the next century despite the
recent shale gas revolution. Thus, renewable and clean energy resources are
urgently required in order to solve global energy and environmental issues
[2, 3]. Among renewable energy resources, solar energy is by far the largest
exploitable resource [1–3]. Nature harnesses solar energy for its production
by photosynthesis, and fossil fuels are the product of photosynthesis [4]. Fossil
fuels range from volatile materials with low carbon:hydrogen ratios such as
methane, to liquids such as petroleum, and to nonvolatile materials composed
of almost pure carbon, such as anthracite coal. The age of the organisms and
their resulting fossil fuels is typically millions of years, and sometimes exceeds
650 million years. The consumption rate of fossil fuels is becoming much faster
than the production rate by nature. Thus, it is quite important to develop arti-
ficial photosynthetic systems for production of solar fuels, which are hopefully
simpler and more efficient than natural systems. The conversion of photon
energy to chemical energy in photosynthesis is achieved by electron transfer
from the excited state of an electron donor (D* : * denotes the excited state) to
an electron acceptor (A) to produce the charge-separated state (D⋅+ –A⋅− ). The
high oxidizing power of D⋅+ in D⋅+ –A⋅− is used for four-electron oxidation of
water to produce dioxygen, whereas the high reducing power of A⋅− is used to
reduce nicotinamide adenine dinucleotide phosphate (NADP+ ) coenzyme to
NADPH [5]. NADPH reduces CO2 by multi-electron reduction to produce sugar
[4, 5]. Thus, electron transfer plays essential roles in photosynthesis. In order
to develop artificial photosynthesis systems, it is quite important to control
electron-transfer systems to maximize the energy conversion.
Electron transfer is the most fundamental chemical reaction in which only elec-
tron is removed or attached. However, it is quite important to recognize the fun-
damental difference of electron-transfer reactions from other chemical reactions
in which chemical bonds are cleaved and formed during the reactions. Because

Electron Transfer: Mechanisms and Applications, First Edition. Shunichi Fukuzumi.

© 2020 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2020 by Wiley-VCH Verlag GmbH & Co. KGaA.
2 1 Introduction

electron transfer occurs based on the Franck–Condon principle, nuclear config-

urations remain the same before and after the electron transfer [6]. In contrast,
nuclear configurations are changed significantly in chemical reactions associated
with the cleavage and formation of chemical bonds. The fastest electron trans-
fer is achieved with no activation energy when the nuclear configurations are
the same before and after the electron transfer with a large driving force of elec-
tron transfer. When the driving force of electron transfer is further increased, the
nuclear configurations are not the same any more before and after the electron
transfer. In such a case, activation energy is again required to change the nuclear
configurations before the electron transfer to be the same as that after the elec-
tron transfer. This means that the rate of electron transfer is slowed down with
increase in the driving force of electron transfer. This region is called the Mar-
cus inverted region, which is discussed in detail later [6]. The importance of the
Marcus inverted region is well recognized in the function of the photosynthetic
reaction center (vide infra) [7–9].
The photoinduced electron-transfer processes occur in a membrane-bound
protein in the photosynthetic reaction center, which contains a number of
cofactors, including four bacteriochlorophylls (BChl) as shown in Figure 1.1
[10]. The central part is referred to as the special pair [(BChl)2 ], while the
other two bacteriochlorophylls (BChl) are referred to as “accessory” bacteri-
ochlorophylls. There are also two bacteriopheophytins (BPhe), two ubiquinones
(QA and QB ), and a non-heme iron atom (not shown in Figure 1.1), which
together with the special pair are organized in pseudo-C2 symmetry forming
two branches (A and B). Light-initiated charge separation occurs between the
special pair [(BChl)2 ] and the neighboring pigments, leading to a radical cation
[(BChl)2 ⋅+ ]. Despite the quasi-symmetrical arrangement of the cofactors, the
electrons are transported unidirectionally along the A-branch of the reaction
center [11–13], which suggests that the symmetry-breaking specific interactions
with the protein are fundamentally important. Light-initiated charge separation
occurs between the special pair [(BChl)2 ] and the neighboring pigment (BPhe),
leading to the radical cation [(BChl)2 ⋅+ ] and the radical anion (BPhe⋅− ). Without
QA , back electron transfer from BPhe⋅− to (BChl)2 ⋅+ occurs with the lifetime of
10 ns to regenerate (BChl)2 and BPhe⋅− . In such a case there is no way for the
energy conversion to occur when the photon energy is only converted to heat.
In the presence of QA , electron transfer from BPhe⋅− to QA occurs at a much
faster rate than the back electron transfer from BPhe⋅− to (BChl)2 ⋅+ despite
the smaller driving force of the electron transfer than that of the back electron
transfer. This has been made possible because of the Marcus inverted region.
The subsequent electron transfer from QA ⋅− to QB also occurs at a much faster
rate than the back electron transfer from QA ⋅− to (BChl)2 ⋅+ because of the much
longer distance between QA ⋅− and (BChl)2 ⋅+ than that between QA ⋅− and QB . The
final charge-separated state [(BChl)2 ⋅+ and QB ⋅− ] is obtained with a nearly 100%
quantum yield, having a lifetime of seconds, which is long enough for further
chemical reactions [14, 15]. Thus, the Marcus inverted region plays a pivotal role
in the charge-separation processes in the photosynthetic reaction center.
As the reverse process of photosynthesis, in which the four-electron oxidation
of water is achieved by using solar energy, the highly exergonic four-electron
 Introduction 3

Me O Me H Me O Me H
H H
Me Et Me Et
N N NH N
Mg
H N N H N HN
Me Me
Me Me
HH HH
O CH3OOC O O CH3OOC O
O O

Bacteriochlorophylls (BChl) Bacteriopheophytin (Bphe)

O
H3CO

H3CO CH3
O
ubiquinone (Q)

B A

BChl

(BChl)2

Bphe

QB QA

Figure 1.1 Cofactors and structure of photosynthetic reaction center of purple bacteria.

reduction of oxygen to water is essential to maintain the life of an aerobic organ-

ism by respiration [16–18]. Cytochrome c oxidases (CcOs) catalyze efficiently
the reduction of molecular oxygen to water by the soluble electron carrier,
cytochrome c [16–18]. In both the four-electron oxidation of water in photosyn-
thesis and the four-electron reduction of O2 in respiration, electron transfer is
accompanied by proton transfer, which is referred to as proton-coupled electron
transfer (PCET) [19–24]. Metal ions also play important roles in controlling
electron transfer in metal ion-coupled electron transfer (MCET) [24–27].
This book describes mechanisms and applications of electron transfer inspired
by electron-transfer processes in photosynthesis and respiration. The first ratio-
nal design of a variety of donor–acceptor covalently linked ensembles including
dyads, triads, tetrads, and pentads is described based on the Marcus theory of
4 1 Introduction

electron transfer, enabling to mimic the energy-transfer and electron-transfer

processes in the photosynthetic reaction center. A specific challenge involves
construction of simple donor–acceptor dyads, which afford longer lived and
higher energy charge separated (CS) states than the natural system. The photo-
synthetic reaction center model compounds can be applied as effective redox
catalysts in various catalytic chemical transformations. Then, the fundamental
concepts of PCET and MCET are discussed and they are applied to developing
efficient catalysts for multi-electron redox processes such as oxidation of water
and reduction of dioxygen and carbon dioxide.
 5

Marcus Theory of Electron Transfer

The dependence of rate constants of electron transfer on the driving force of

electron transfer is well analyzed on the basis of the Franck–Condon principle
(vide supra) by the Marcus theory of electron transfer, which provides basic prin-
ciples to analyze the rate constant of electron transfer quantitatively [6]. Accord-
ing to the Marcus theory of electron transfer [6], the rate constant of nonadiabatic
intramolecular electron transfer (k ET ) is given by Eq. (2.1):
( )1∕2 [ ]
4𝜋 3 2 (ΔGET + 𝜆)2
kET = V exp − (2.1)
h2 𝜆kB T 4𝜆kB T
where V is the electronic coupling matrix element, h is the Planck constant, T is
the absolute temperature, ΔGET is the free energy change of electron transfer, and
𝜆 is the reorganization energy of electron transfer [6]. The ΔGET values are deter-
mined from the one-electron oxidation potentials (Eox ) of electron donors (D)
and the one-electron reduction potentials (Ered ) of electron acceptors by Eq. (2.2):
ΔGET = e(Eox − Ered ) (2.2)
where e is elementary charge. According to Eq. (2.1), the logarithm of the
electron-transfer rate constant (log k ET ) is related parabolically to the driving
force of electron transfer from electron donors to acceptors (−ΔGET ) and the
reorganization energy (𝜆) of electron transfer, that is, the energy required to
structurally reorganize the donor, acceptor, and their solvation spheres upon
electron transfer [6].
When the magnitude of the driving force of electron transfer becomes the
same as the reorganization energy (−ΔGET = 𝜆), the electron-transfer rate
reaches a maximum and is basically controlled by the magnitude of electronic
coupling (V ) between the donor and acceptor moieties (Eq. (2.1)). Upon passing
this thermodynamic maximum, the highly exothermic region of the parabola
(−ΔGET > 𝜆) is entered, in which an additional increase of the driving force
results in an actual slowdown of the electron-transfer rate, due to an increasingly
poor vibrational overlap of the product and reactant wave functions. This
highly exergonic range is generally referred to as the Marcus inverted region
[6–8, 28, 29]. In such a case, the magnitude of the reorganization energy is
the key parameter to control the electron-transfer process. The smaller the
reorganization energy, the faster is the forward photoinduced charge-separation

Electron Transfer: Mechanisms and Applications, First Edition. Shunichi Fukuzumi.

© 2020 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2020 by Wiley-VCH Verlag GmbH & Co. KGaA.
6 2 Marcus Theory of Electron Transfer

e–
λsmall
∗
D A λlarge
Charge
separation
(CS) Fast CS
kCS

log kET
–
e
+ –
hν D A
kCR
Slow CR
Charge
recombination
(CS)
D A 0 –ΔGCS –ΔGCR
–ΔGET

Figure 2.1 (a) Schematic diagram of photoinduced electron transfer of an electron

donor–acceptor (D–A) dyad. (b) Driving force dependence of log kET with different 𝜆 values
(for the meaning of 𝜆, see text).

(CS) process, but the charge-recombination (CR) process becomes slower

when the driving force for back electron transfer (–ΔGET ) is larger than the
reorganization energy (𝜆) of electron transfer as shown in Figure 2.1. Among
the key parameters that govern electron-transfer reactions (V , ΔGET , and 𝜆),
the reorganization energy (𝜆) imposes the most important impact. The primary
electron-transfer processes of photosynthesis are, for example, characterized by
an extremely small reorganization energy (𝜆 ∼ 0.2 eV), attained by the protein
environment. This aspect is essential to achieving ultrafast charge separation and
retarding the energy-wasting charge recombination, which is highly exergonic
(−ΔG = 1.2 eV) [11–15]. Thus, the components of artificial photosynthesis,
which are not necessarily natural components in photosynthesis, must have
small 𝜆 values of electron transfer.
 7

Photosynthetic Reaction Center Models

The first candidates of artificial photosynthetic reaction centers are porphyrins,

which have been involved in a number of important biological electron-transfer
systems including the primary photochemical reactions of chlorophylls in the
photosynthetic reaction centers. Porphyrins contain an extensively conjugated
two-dimensional π-system and are thereby suitable for efficient electron trans-
fer, because the uptake or release of electrons results in minimal structural and
solvation change upon electron transfer, resulting in a small 𝜆 value of electron
transfer [30]. In addition, rich and extensive absorption features of porphyrinoid
systems guarantee increased absorption cross sections and efficient use of the
solar spectrum [30]. In contrast with the two-dimensional porphyrin π-system,
fullerenes contain an extensively conjugated three-dimensional π-system [31].
Electron transfer to C60 is highly efficient because of the minimal changes of
structure and solvation associated with the electron-transfer reduction [31–33].
Thus, a series of porphyrin–fullerene linked molecules have been designed and
synthesized to mimic the charge-separation processes in the photosynthetic reac-
tion center, starting from a zinc porphyrin–C60 dyad (ZnP–C60 ), a ferrocene–zinc
porphpyrin–C60 triad (Fc–ZnP–C60 ), a zinc porphyrin-free base porphyrin–C60
triad, up to a tetrad (Fc–ZnP–H2 P–C60 ) [34–39].
The driving force dependence of the electron-transfer rate constants (k ET )
of these dyad, triad, and tetrad molecules for CS and CR processes is shown
in Figure 3.1, where log k ET is plotted against the driving force (−ΔGET ) [39].
The lines in Figure 3.1 represent the best fit to Eq. (2.1) (ZnP–C60 : 𝜆 = 0.66 eV,
V = 3.9 cm−1 ; Fc–ZnP–C60 , Fc–H2 P–C60 , and ZnP–H2 P–C60 : 𝜆 = 1.09 eV,
V = 0.019 cm−1 ; Fc–ZnP–H2 P–C60 : 𝜆 = 1.32 eV, V = 0.00017 cm−1 ) [39]. The
𝜆-value increases, whereas the V value decreases with increasing edge-to-edge
distance in the order of the dyad (Ree = 11.9 Å), the triad (Ree = 30.3 Å), and the
tetrad (Ree = 48.9 Å). Such an increase in the 𝜆 value with increasing distance
results from an increase in the solvent reorganization energy (𝜆s ), because the 𝜆s
value is known to increase with increasing distance between an electron donor
and an acceptor as given by Eq. (3.1):

𝜆s = e2 [(2r1 )−1 + (2r2 )−1 − (r12 )−1 ][n−2 − (es )−1 ] (3.1)

where r1 and r2 are the radii of the donor and acceptor, r12 is the donor–acceptor
distance, 𝜀 is the dielectric constant, and n is the refractive index [6, 40].

Electron Transfer: Mechanisms and Applications, First Edition. Shunichi Fukuzumi.

© 2020 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2020 by Wiley-VCH Verlag GmbH & Co. KGaA.
8 3 Photosynthetic Reaction Center Models

Me
Me
N N N
N N N NHCO M CONH
Zn CONH Fe N N
N N

Fc–C60 Fc–ZnP–C60(M= Zn) Fc–H2P–C60(M=H2)

Me
N N NH N N
CONH Zn NHCO CONH
Fe N N N HN

Fc–ZnP–H2P–C60

12

10

Dyad

8
log kET(s–1)

4 Triad

Tetrad
0
0 0.5 1.0 1.5
–ΔGET(eV)

Figure 3.1 Driving force (−ΔGET ) dependence of intramolecular electron-transfer rate

constants (kET ) in ZnP–C60 (CS [○]; CR [◽]), Fc–ZnP–C60 (•), Fc–H2 P–C60 (▴), ZnP–H2 P–C60 (◾),
and Fc–ZnP–H2 P–C60 (△). Source: Imahori et al. 2001 [39]. Reproduced with permission of
American Chemical Society.
 Photosynthetic Reaction Center Models 9

Figure 3.2 Edge-to-edge distance (Ree ) 15

dependence of optimal electron-transfer rate
constants (log[kET (optimal)/s−1 ]) in ZnP–C60 β = 0.60 Å–1

log kET (optimal) (s–1)

dyad, Fc–ZnP–C60 triad, Fc–H2 P–C60 triad, 10 V0 = 210 cm–1
ZnP–H2 P–C60 triad, and Fc–ZnP–H2 P–C60 tetrad. Dyad
The line represents the best fit to Eq. (2.1)
(𝛽 = 0.60 Å−1 , V 0 = 210 cm−1 ). 5
Triad

0
Tetrad

–5
0 20 40 60
Ree (Å)

In the case of the dyad, the CR rate in ZnP⋅+ –C60 ⋅− in the Marcus inverted
region is much slower than the CS rate constants from both the singlet and triplet
excited states in the Marcus normal region (Figure 3.1). This enables subsequent
electron transfer from Fc to ZnP⋅+ in the triad (Fc–ZnP⋅+ –C60 ⋅− ) and from ZnP
to H2 P⋅+ in ZnP–H2 P⋅+ –C60 ⋅− to produce the final CS state, Fc+ –ZnP–C60 ⋅−
and ZnP⋅+ –H2 P–C60 ⋅− , in competition with the back electron transfer in the
initial CS states. In the case of Fc+ –ZnP–H2 P–C60 ⋅− , the charges are separated
at a long distance (Ree = 48.9 Å) [39]. The lifetime of the resulting CS state at
such a long distance in a frozen benzonitrile (PhCN) has been determined as
0.38 seconds [39]. Similar tetrad and pentad compounds were reported to attain
long-lived CS states up to 1.7 seconds [40–42]. It should be noted that the CS
lifetime is temperature independent, since the CR process is at the Marcus top
region (Figure 3.1) [39]. This is the first example to achieve a CS lifetime that is
comparable to that observed for the bacterial photosynthetic reaction center.
However, such an extremely long CS lifetime could only be determined in frozen
media, since in condensed media bimolecular back electron transfer between
two Fc+ –ZnP–H2 P–C60 ⋅− is much faster than the unimolecular CR process [39].
The maximum k ET values (k ETmax ) of dyads, triads, and tetrads in the Marcus
plot (Figure 3.2) are correlated with the edge-to-edge distance (Ree ), separating
the radical ions, according to Eq. (3.2) [39]:
( 3∕2 2 )
2𝜋 V0
ln kETmax = ln − 𝛽Ree (3.2)
h(𝜆kB )1∕2
where V 0 refers to the maximal electronic coupling element, while 𝛽 is the decay
coefficient factor (damping factor), which depends primarily on the nature of the
bridging molecule. From the linear plot of ln k ETmax vs. Ree the 𝛽 value is obtained
as 0.60 Å−1 [39]. This 𝛽 value is located within the boundaries of nonadiabatic
electron transfer reactions for saturated hydrocarbon bridges (0.8–1.0 Å−1 ) and
unsaturated phenylene bridges (0.4 Å−1 ) [43].
10 3 Photosynthetic Reaction Center Models

hν hν hν

e– Ar Ar Ar e–

CH3
N N N N N N N
NHCO Zn Zn Zn CONH
Fe N N N N N N

Ar Ar Ar τ = 0.53 s

Fc–(ZnP)3–C60

Scheme 3.1 Multistep photoinduced electron transfer in a ferrocene-meso, meso-linked

porphyrin trimer–fullerene pentad (Fc–(ZnP)3 –C60 ); Ar = 3,5-But 2 C6 H3 . Source: Imahori et al.
2004 [44]. Reproduced with permission of John Wiley & Sons.

The best molecule mimicking multistep electron-transfer processes in the pho-

tosynthetic reaction center so far reported is a ferrocene-meso, meso-linked por-
phyrin trimer–fullerene pentad (Fc–(ZnP)3 –C60 in Scheme 3.1), where the C60
and the ferrocene (Fc) are tethered at both the ends of (ZnP)3 (Ree = 46.9 Å) [44].
The lifetime of the final CS state (0.53 seconds at 163 K) has been attained without
lowering the CS efficiency (Φ = 0.83) [44].
 11

Electron Donor–Acceptor Dyads

Multistep electron-transfer processes have been utilized to attain a long distance

charge separation (CS), mimicking the natural photosynthetic reaction center
(vide supra). However, a significant amount of energy is lost during the multistep
electron-transfer processes to reach the final CS state [11–15]. In photosynthe-
sis a two–step photoexcitation, the so-called “Z-scheme,” is thereby required to
recover the energy loss via the multistep electron-transfer processes and to gain
strong oxidizing power to oxidize water as well as high reducing power to reduce
NAD+ coenzyme [4]. The design and synthesis of molecular machinery mimick-
ing such an elaborated “Z-scheme” in nature seems far beyond our capability,
and even if it could be done, the synthetic cost would certainly preclude any
type of practical application. Thus, it is highly desired to design simple molec-
ular electron donor–acceptor dyads that are capable of fast CS but can retain
slow charge recombination (CR). Theoretically, it is possible to obtain such an
electron donor–acceptor dyad, because the CS lifetime increases with increas-
ing driving force of electron transfer in the Marcus inverted region (vide supra).
However, the driving force of electron transfer should be lower than the triplet
excited state of one of the components of donor–acceptor dyads. Otherwise, the
CS state would decay rapidly to the triplet excited state in the Marcus normal
region rather than to the ground state in the Marcus inverted region [35].
A number of simple donor–acceptor dyads have been designed and synthe-
sized to attain long-lived CS state, where the donor and acceptor molecules are
linked with a short spacer to minimize the solvent reorganization energy [45–50].
Efficient photoinduced electron transfer occurs in a zinc imidazoporphyrin–C60
dyad (ZnImP–C60 ) with a short linkage to form the CS state (ZnImP⋅+ –C60 ⋅− )
with the rate constant of 1.4 × 1010 s−1 (Scheme 4.1) [45]. The CS state (1.34 eV)
is lower in energy than both the triplet excited states of C60 (1.50 eV) and ZnImP
(1.36 eV) [45]. The CS state, produced upon photoexcitation of ZnImP–C60 , is
detected by the transient absorption spectrum, which has absorption bands at
700 and 1040 nm due to ZnImP⋅+ and C60 ⋅− , respectively [45]. The CS state decays
by back electron transfer to the ground state, obeying first-order kinetics with a
rate constant of 3.9 × 103 s−1 (the lifetime is 260 μs) at 298 K [45]. At 278 K the life-
time of the CS state was determined as 310 μs, which is much longer than those
of conventional donor–acceptor dyads with longer spacers [7–9].

Electron Transfer: Mechanisms and Applications, First Edition. Shunichi Fukuzumi.

© 2020 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2020 by Wiley-VCH Verlag GmbH & Co. KGaA.
12 4 Electron Donor–Acceptor Dyads

+
Ar Ar Me Ar Ar Me
N hν N
N N N N
N M N N M N –
N N
N H N H
Ar Ar Ar Ar

ZnlmP–C60 Cs lifetime: 310 μs (278 K)

Scheme 4.1 Formation of a long-lived CS state of a zinc imidazoporphyrin–C60 dyad

(ZnImP–C60 ) with a short linkage (Ar = 3,5-But 2 C6 H3 ). Source: Kashiwagi et al. 2003 [45].
Reproduced with permission of American Chemical Society.

An electron donor–acceptor dyad linked with a short spacer containing Au(III)

and Zn(II) porphyrins (ZnPQ–AuPQ+ in Scheme 4.2) also affords a long-lived
electron-transfer state with a lifetime of 10 μs in nonpolar solvents such as cyclo-
hexane [46]. The introduction of quinoxaline to the gold porphyrin results in a
lowering of the electron-transfer state energy. In contrast to the case of neutral
donor–acceptor dyads, the energy of the electron-transfer state (ZnPQ⋅+ –AuPQ)
becomes smaller in a less polar solvent, which is lower than the energies of the
triplet excited states of ZnPQ (1.32 eV) and AuPQ+ (1.64 eV) [46]. Photoinduced
electron transfer occurs from the singlet excited state of the ZnPQ (1 ZnPQ* ) to
the metal center of the AuPQ+ moiety to produce ZnPQ⋅+ –AuII PQ. The observed
long lifetime of ZnPQ⋅+ –AuII PQ results from a small reorganization energy for
the metal-centered electron transfer of AuPQ+ in nonpolar solvents due to the
small change in solvation upon electron transfer as compared with that in polar
solvents [46]. In a polar solvent such as benzonitrile (PhCN), no CS state was
observed, but instead only the triplet–triplet absorption due to 3 ZnPQ* –AuPQ+
was observed [46]. The absence of an observable CS state in PhCN is ascribed to
the much slower photoinduced electron transfer due to the large reorganization

+
Ar Ar
N N
Ar Ar
N N Au N
N N
N Zn N N
N Ar Ar
N
Ar Ar Ar Ar
ZnPQ–AuPQ+ +
N N
Ar Ar
N N Au N
hν N N
N Zn N N
N Ar Ar
N
Ar Ar

Long-lived charge-separated state in nonpolar solvents

Scheme 4.2 Formation of a long-lived CS state of ZnPQ–AuPQ+ in nonpolar solvents

(Ar = 3,5-But 2 C6 H3 ). Source: Fukuzumi et al. 2003 [46]. Reproduced with permission of
American Chemical Society.
 Electron Donor–Acceptor Dyads 13

ZnCh–C60
Me
2.6 Å
N
Me
Me Et
N N
Zn
H N N
Me
Me
H
MeO2C O N O

Hexyl
ZnCh

Figure 4.1 Structure of a closely linked ZnCh–C60 dyad. Source: Ohkubo et al. 2004 [47].
Reproduced with permission of John Wiley & Sons.

energy as compared with that in nonpolar solvents allowing an efficient intersys-

tem crossing process in the ZnPQ–AuPQ+ dyad to produce the triplet excited
state 3 ZnPQ* –AuPQ+ [46].
A closely linked zinc chlorin–fullerene dyad (ZnCh–C60 in Figure 4.1) affords
a longer CS lifetime as compared with other zinc chlorin–fullerene dyads with
longer spacers [47–51]. A deoxygenated PhCN solution containing ZnCh–C60
gives rise upon a 388 nm laser pulse to a transient absorption maximum at 460 nm
due to the singlet excited state of ZnCh [47]. The decay rate constant was deter-
mined as 1.0 × 1011 s–1 , which agrees with the value determined from the fluo-
rescence lifetime measurements [47]. The decay of absorbance at 460 nm due to
1
ZnCh* is accompanied by an increase in absorbance at 590 nm due to ZnCh⋅+
[47]. This indicates that electron transfer from 1 ZnCh* to C60 occurs rapidly to
form the CS state, ZnCh⋅+ –C60 ⋅– . The CS state decays via back electron transfer
to the ground state rather than to the triplet excited state, because the CS state is
lower in energy (1.26 eV) than the triplet excited states of both C60 (1.50 eV) and
ZnCh (1.36–1.45 eV) [47]. The lifetime of the CS state is determined as 230 μs at
298 K. The large temperature dependence of the CS lifetime is observed and the
lifetime of the CS state at 123 K becomes as long as 120 seconds [47].
Covalently and non-covalently linked porphyrin–quinone dyads constitute one
of the most extensively investigated photosynthetic reaction center models, in
which the fast photoinduced electron transfer from the porphyrin singlet excited
state to the quinone occurs to produce the CS state, mimicking well the photo-
synthetic electron transfer [52–54]. Unfortunately, the CR rates of the CS state
of porphyrin–quinone dyads are also fast and the CS lifetimes are mostly on
the order of picoseconds or subnanoseconds in solution [52–54]. In general, a
three-dimensional C60 is superior to a two-dimensional quinone in terms of the
smaller reorganization of electron transfer of C60 as compared with quinone (vide
supra) to attain the long-lived CS state [31–33, 55]. When the geometry between
a porphyrin ring and quinone is optimized by using hydrogen bonds, which can
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