Artificial photosynthesis
We raise here a series of critical issues regarding artificial
photosynthesis with the intention of increasing awareness about what
needs to be done to bring about a working prototype. Factors under
consideration include energy and electron transfers, coupled redox
reactions, repair mechanisms, and integrated photosystems.
Andrew C. Benniston and Anthony Harriman*
Molecular Photonics Laboratory, School of Chemistry, Bedson Building, Newcastle University, Newcastle upon Tyne NE1 7RU, UK
*E-mail: anthony.harriman@ncl.ac.uk
Natural photosynthesis, the process whereby CO2 is converted
into carbohydrate and water is oxidized to molecular oxygen, has
supplied the overwhelming majority of stored energy available
on our planet1. This stored energy, which is mostly in the form
of fossil fuels, had sufficed for billions of years and it is only
very recently that the stocks of fuel have started to deplete at
a rate faster than Nature can replenish2,3. Indeed, our insatiable
appetite for instant energy is set to expand at an unprecedented
pace and our capability to generate CO2 knows no bounds. The
need to provide additional energy and to deal with the ensuing
ecological problems associated with current lifestyles in the
developed world pose tremendous challenges for the scientific
community4. The urgency, and therefore the funding, devoted to
solving these problems is set exclusively by the price of oil and, as
a consequence, the attention given to meeting these challenges
is driven by market forces. Once again we are entering a period
of wildly fluctuating oil prices and this time, unlike the 1970s,
it is unlikely that the cost per barrel will fall steeply after an
uncomfortable ride. The search for renewable energy supplies
is now a major issue for all stable governments but it must be
accompanied by new initiatives to reduce CO2 levels and, in as
much as it is possible, sequester CO2 from the atmosphere. This is
26 DECEMBER 2008 | VOLUME 11 | NUMBER 12
precisely how photosynthesis works and although many intriguing
alternatives merit consideration at a local level, it is crucial that
scientists are given the opportunity to produce a viable form of
artificial photosynthesis. The overall challenge is massive and
needs to be addressed by a multinational force dedicated to the
task – it is far beyond the capability of a single investigator.
Most of the chemistry associated with natural photosynthesis is
understood at a reasonably precise level5. The reagents, chemical
reactions, rates, and mechanisms have been known for decades6,7 and
although refinements continue to be made, the basic understanding
is in place8. Likewise, the structure and level of organization of
the essential features of photosynthesis have been elucidated by
biophysicists and further defined by protein crystallography (a full
compendium of X-ray-determined structures of membrane proteins
can be found at http://www.mpibp-frankfurt.mpg.de/michel/public/
memprotstruct.html) and advanced theory9. How can we utilize this
information to engineer an artificial leaf? This is the key question
and the answer is that no one knows. We can, however, set out the
state of current knowledge and thereby expose the main challenges
that remain. In so doing, we emphasize the underlying chemistry. Our
rationale for this approach is that we need first to devise suitable
chemical processes before attempting to build working prototypes. The
ISSN:1369 7021 © Elsevier Ltd 2008
 Artificial photosynthesis REVIEW

engineering principles, daunting in themselves, need to be developed
once the chemistry is in place.
Capturing the photons
Sunshine is diffuse and although sufficient sunlight reaches the surface
of the Earth to satisfy all our energy needs, it must be concentrated
at some stage in the overall storage process. Nature accomplishes this
essential task by using light-harvesting complexes to collect incident
photons, move them over large distances and direct them to a site
where the chemistry takes place10. The light-harvesting complex is
a highly organized array of chlorophyll molecules as illustrated in
Fig. 111. Many such arrays act cooperatively both to shuttle photons
to the right place and to avoid the problems of overload at high
light intensity. The structural elegance and chemical efficacy of the
natural system have stimulated great interest in artificial analogs,
mostly involving porphyrin-based chromophores12. Nature has opted
to transfer excitation energy between weakly coupled chromophores
via the so-called Förster mechanism13, which involves through-space
interactions, but artificial systems tend to supplement this route with
electron exchange interactions occurring within more strongly coupled
chromophoric arrays14. A crucial feature of all such systems is the
need to avoid involvement of triplet states, since these will inevitably
transfer energy to oxygen and form the highly destructive species
known as singlet molecular oxygen15. This latter metastable reagent
is responsible for rapid aging and ultimate destruction of the photon
collector.
The first artificial photon collectors comprised covalently linked
porphyrin dimers that displayed highly efficient excitation energy
transfer over short distances16. These were followed by detailed studies
of clusters, arrays, dendrimers, and polymers. More recently, extremely
long, porphyrin-based ribbons have been reported17 and attempts have
been made to develop porphyrin-based wheels and rings18. In all cases,
electronic energy transfer is fast and highly efficient. There is, however,
an additional requirement in that energy produced following excitation
must percolate through the system to terminate preferably on a single
chromophore19. By ensuring that an energy gradient is set up within
a molecular system, this cascade effect is readily achievable but does
require careful design and choice of chromophores. A fine example of
this is the molecular array shown in Fig. 220, which comprises four
different, yet complementary, organic chromophores. The color code
attempts to show the internal energy gradient in that the fluorene
molecule (blue) absorbs high-energy photons and the bodipy (red) is
the terminus. The arrows show the pathways for energy migration
depending on which chromophore is illuminated. It is worth noting that
essentially all absorbed photons terminate at the bodipy unit.
The natural system is highly ordered but this is not true for most
artificial prototypes, despite their synthetic attractiveness. The first
attempts to create ordered networks for electronic energy transfer
were described by Mobius and Kuhn21 and involved monomolecular
layers of cyanine dyes coated onto transparent slides. Other reports
have focussed on energy transfer in polymeric media, leading to the
development of solar concentrators of the type illustrated in Fig. 322.

(a) (b)

Fig. 1 Representation of the X-ray structure of bacterial light-harvesting complexes. (a) Ring of 18 B850 bacteriochlorophyll-a molecules and (b) ring of nine B800
bacteriochlorophyll-a molecules with a different ring between the helices of the apoproteins. The α-apoproteins are colored yellow and the β-apoproteins green.
Electronic energy is transferred around the ring, between cofacial pigments, in an incoherent manner until it migrates to a different ring. Eventually, the photon
reaches a light-harvesting complex with a reaction center complex embedded in its center. (Reproduced by permission of McDermott et al.11.)

DECEMBER 2008 | VOLUME 11 | NUMBER 12 27

REVIEW Artificial photosynthesis
Fig. 2 A tailor-made artificial light-harvesting array based on fluorene (blue), pyrene (purple), perylene (green), and bodipy (red) units. Each unit is selected for its
complimentary absorption profile. Arrows depict the pathways for energy migration to the terminal unit. Note that a wide spectral range is harvested in this way,
with essentially every absorbed photon being directed to the bodipy core. In this case, energy occurs by way of both through-space and through-bond processes,
unlike in the natural system, as indicated in the insert.
Fig. 3 Example of an organic solar concentrator in the form of a very low
concentration of dye dispersed in a polymeric film and coated onto a glass
surface. The upper panel was taken without illumination while the lower panel
shows fluorescence from the thin film. Note how the fluorescence is localized
at the edge.
More recently, attention has turned to the possibility of energy transfer
occurring in crystalline media. Thus, although the dyad23 shown in
Fig. 4 is not as elaborate as the multichromophore systems outlined
above, it operates as a photon collector in the crystalline state by
28 DECEMBER 2008 | VOLUME 11 | NUMBER 12
transferring energy from the p-quaterthiophene residue (yellow) to
the bodipy core. The energy-transfer rate increases six-fold when the
dyad is dispersed in a soft glass. Considering that artificial systems will
be required to operate in the solid state, these results are encouraging
for creating models using the bodipy chromophore. Furthermore, since
thiophene groups are easily polymerized, the manufacture of polymeric
materials looks entirely feasible. Finally, we note the novel experiments
reported by Calzaferri and coworkers24,25 using dye-loaded zeolites.
Here, rationally designed dyes are either incorporated into channels
inside the zeolite or used to block the pore. Energy transfer can then be
directed along the channel. Quite separately, research has progressed
into the design of light-harvesting units for dye-injection solar cells of
the type pioneered by Grätzel26. Here, a dye sensitizer is used to inject
charge into nanostructured surfaces such as fractal TiO2 in contact with
a suitable redox-active electrolyte. Considerable work has gone into the
optimization of the photon-collecting properties of the sensitizers27–31
and into engineering the cells for stable performance32–35. Further
attention has been paid to photon collectors for low band-gap organic-
based solar cells36–40 and many of the basic concepts are common to
all types of light harvesters.
Charge separation
The light-harvesting complex directs photons to a Reaction Center
Complex (RCC) where the absorbed photon is used to drive an
electron-transfer reaction that leads to charge separation across a
 Artificial photosynthesis REVIEW

Fig. 4. Illustration of a bodipy-based molecular dyad used for studying intramolecular electronic energy transfer, and the crystal packing diagram of the molecules
as determined by X-ray crystallography. UV photons absorbed by the oligothiophene unit are transferred efficiently to the bodipy dye, which fluoresces strongly,
despite the orthogonal connection. Energy transfer becomes more efficient as the orthogonality is relaxed. Color code: S = yellow, B = orange, F = green, N = blue,
C = gray. (Reproduced in part by permission of Benniston et al.23.)

biological, lipid bilayer membrane (Fig. 5)41. Nature has evolved this
cascade-type effect in which the electron and positive hole move
further apart through a series of short-range jumps as a means
to circumvent rapid charge recombination between the electron
and hole. Research into artificial analogs of the natural RCC has
advanced rapidly, aided by elegant theoretical models42,43, stimulated
by studies of the crystal structure of the bacterial RCC44,45, and
facilitated by tremendous advances made in our understanding of
simple electron-transfer processes by pioneers such as Mataga46,
Closs47, and Wasielewski48. Early work on artificial versions of the
RCC used porphyrin–quinone dyads but these suffered from fast
charge recombination49. The essential breakthrough was made by
Gust et al.50, who reported the first molecular triad, based on the
realization that the rate of electron transfer decreases exponentially

Fig. 5. Spatial arrangement of the cofactors in the photosynthetic reaction center complex of the purple bacteria Rhodobacter sphaeroides, as determined by X-ray
crystallography. Photons arrive at a special pair of bacteriochlorophyll molecules (green), by way of the light-harvesting complex. Electron transfer then occurs,
first to the monomeric bacteriochlorophyll (blue) and subsequently to the free-base bacteriopheophytin (red), then to the first quinone (yellow, QB) and finally to
the second quinone (purple, QA). There is an iron center associated with the quinone residues. By way of such a cascade of electron-transfer steps, transmembrane
electron transfer is achieved. Note the symmetry of the tetrapyrrole-based cofactors, but it should be realized that electron transfer occurs exclusively along the
right-hand branch. (Reproduced by permission of Dr R. Wheeler.) The insert shows how the RCC fits inside one of the light-harvesting rings.

DECEMBER 2008 | VOLUME 11 | NUMBER 12 29

REVIEW Artificial photosynthesis

Fig. 6 Simplified energy-level diagram showing the principle of charge separation via sequential electron-transfer steps. Excitation leads to formation of the singlet-
excited state localized on the chromophore, which is also the primary donor (D1). In competition with fluorescence, charge separation occurs to form the radical
ion pair in which an electron has been transferred to the primary acceptor (A1). Secondary electron transfer to form the extended radical ion pair can compete
with charge recombination to reform the ground state. Provided the thermodynamics can be satisfied, hole transfer can occur to move the oxidizing equivalent to
the secondary donor (D2). Charge recombination is now very slow because of the large distance separating the charges. Note that a certain fraction of the initial
excitation energy is lost at each stage.

with increasing separation between the reactants. This has led to the
introduction of countless triads51, tetrads52, pentads53, etc., that are
loosely modeled on the architecture of the RCC but allow for the fact
that there is no need to accurately duplicate all the structural facets.
The basic idea is to move electrons from one side of the supermolecule
to the other side as quickly and as efficiently as possible, so that the
positive and negative charges become spatially remote. It is important
to realize that simply making long molecules is not the answer to the
charge-recombination problem and careful choice of the individual
units is essential (Fig. 6). Considering the time and effort required to
synthesize elaborate multicomponent molecules, the wrong design
could be disastrous. Even so, some superb molecular structures have
been described that closely resemble the natural RCC, often having the
quinone replaced with a fullerene derivative.
A great variety of molecular dyads have been synthesized in order
to critically examine various aspects of electron-transfer theory. These
have included weakly associated conjugates, such as the hydrogen-
bonded systems reported primarily by Sessler et al.54, as well as
covalent analogs. A persistent line of enquiry has been to pursue
unusually long-lived charge-separated states without the need for
extended synthesis. All such attempts have failed, although there have
been several erroneous reports to the contrary55. This has necessitated
the formulation of a set of ‘rules’ that must be fulfilled in order to
claim a long-lived, charge-separated state56. The advantages of such
simple dyads are obvious but something rather special is needed to
circumvent the inherently fast rates of charge recombination, especially
when dealing with high-energy states able to form triplet species57.
Unfortunately, this ‘special ingredient’ has defied identification and
there are many who doubt its existence! The situation is illustrated in
Fig. 7.
It is evident that the final design of a molecular system for artificial
photosynthesis will require the coupling of the light-harvesting

Fig. 7 Simplified energy diagram showing processes that take place following illumination of a molecular dyad. Excitation results in formation of the singlet-excited
state localized on the chromophore, which is also the primary electron donor. This species can fluoresce but can also transfer an electron to an appended acceptor,
forming a charge-separated state. In turn, this latter species can decay via charge recombination or undergo intersystem crossing to form a triplet-excited state
localized on either donor or acceptor. The triplet is liable to transfer energy to oxygen, forming the highly dangerous species, singlet molecular oxygen.

30 DECEMBER 2008 | VOLUME 11 | NUMBER 12

 Artificial photosynthesis REVIEW

portion to the artificial reaction center. The example shown in Fig. 858
utilizes a unique combination of zinc and free-base porphyrins and an
electron-affinic C60 terminal. Selective illumination of the peripheral
zinc porphyrin causes energy migration first to the central group
and then to the free-base porphyrin shown in green. The resultant
excited state transfers an electron to C60 in about 25 ps. The positive
hole formed initially on the free-base porphyrin migrates to the zinc
porphyrin under thermodynamic control to create a charge-separated
state in high yield that survives for 25 μs. This is sufficient time to
allow useful catalytic processes to compete with long-range charge
recombination.
As with electronic energy transfer, the question must be posed as
to how it is possible to impose directionality on the electron-transfer
event. Again, the first rationale attempts to study electron transfer in
organized media were made by Kuhn59, with his Langmuir–Blodgett
films. Modified enzymes have been prepared by several groups and
employed to direct an electron from a donor on the surface to a
specific site within the protein. Such experiments have led to a deeper
understanding of how electrons tunnel through protein matrices60.
Others have assembled molecular dyads around DNA duplexes and
thereby set up one-dimensional electron-transfer pathways61. More
elaborate systems have been used to pump electrons across liposomes
and membranes, and in particular Gust et al.62 have been highly
successful in this field. The key puzzle, however, is how to extend
such work to engineer photoactive films with oriented arrays of
multicomponent supermolecules that can be printed on large surface
areas and that retain the activity of isolated molecules in a polar
solvent. Building ever more intricate molecular systems that closely
resemble the structural features of the RCC is an interesting academic
challenge but gets us no nearer to a successful artificial photosynthetic
system. Some success has been achieved with self-assembled π-stacks,
but these lack the true element of directionality needed to drive
photochemical water cleavage. At this time, artificial photosynthesis
lags far behind photoelectrochemical systems, such as organic
photovoltaics63,64 or dye-injection solar cells65, and it is clear that new
initiatives are urgently needed.
Photocatalytic cycle
Photochemistry provides direct access to potent oxidizing or reducing
species that can be used to drive redox reactions, leading to useful
chemical feedstocks. There are two inherent problems to overcome.
Firstly, the species generated by photolysis are the result of one-
electron transfers but formation of stable chemicals requires at
least two, and often four or more, electrons. As such, some kind of
charge accumulation is needed to couple the photochemical steps to
product formation. Secondly, to avoid back-reactions between the

Fig. 8 Illustration of a molecular array that acts as both a photon collector and an artificial reaction center. Arrows show pathways for energy migration to the
terminal free-base porphyrin, from where electron transfer to the attached C60 residue takes place. The resultant charge-separated state is susceptible to fast
charge recombination, during which the excitation energy is converted into heat, but hole transfer (ht) occurs from the free-base porphyrin π-radical cation to one
of the appended zinc porphyrins. In this way, the charges become spatially isolated and the rate of charge recombination decreases. For the example shown, the
lifetime of the charge-separated state is 25 μs.

DECEMBER 2008 | VOLUME 11 | NUMBER 12 31

REVIEW Artificial photosynthesis
photochemical products, it is necessary to design and subsequently link
two separate cycles – one forming a fuel and the other providing the
all-important oxidizing agent. Using water as the electron source, for
example, individual photosystems would be engineered to produce H2
and O2 but they would need to be connected via a common relay.
In fact, many individual photocycles have been optimized for the
generation of certain small molecules. Photochemical generation of H2
from organic substrates in the presence of a suitable electron-storage
catalyst is trivial66. The catalyst can be a precious metal colloid67 or
an enzyme68 and the system can be made to work extremely well;
the example shown in Fig. 9 is the most advanced photosystem
of this type69. It stops only when the chromophore has been fully
hydrogenated or when the substrate runs out. Suitable substrates
might be waste materials or glycerol left over from biofuel production.
It is much more difficult to identify suitable catalysts for CO2 reduction
and even more so for NH3 formation. This latter reaction would be
an ideal way to generate cheap supplies of fertilizer for developing
countries but there are no viable systems known at the present time.
Likewise, the photooxidation of persulfate to O2 has been perfected
using a range of chromophores and with colloidal RuO2 or IrO2
as catalyst70. Turnover numbers tend to be modest and the harsh
experimental conditions destroy the chromophore. Prolonged attempts
to replace the colloidal redox catalyst with simpler molecules able to
undergo several changes in oxidation state, most notably manganese
porphyrins, have not been successful71. Indeed, now that the structure
of the natural O2-evolving catalyst is available72–74, it is clear that
there are no artificial analogs. The search for improved oxidation
catalysts continues75–80. Milder conditions can be used for halide
oxidation and this is a viable alternative to O2 production, especially
using seawater as the substrate.
Producing a mixture of gaseous H2 and O2 is clearly undesirable81
and there are major problems involved in collecting H2 evolved over
Fig. 9 Advanced photosystem for the photochemical dehydrogenation of ethanol. The photoactive ingredient is a tin(IV) porphyrin and the primary donor is NADH.
This latter species is regenerated using alcohol dehydrogenase (ADH) as selective catalyst. The reduced porphyrin is used to chemically reduce methyl viologen
(MV2+). This latter species is recovered in a separate catalytic process in which colloidal Pt reduces water to H2. The net reaction is the conversion of ethanol to
acetaldehyde and H2 gas. The system is shown as a two-electron cycle.
32 DECEMBER 2008 | VOLUME 11 | NUMBER 12
a wide area. The only realistic option is to couple O2 generation with
the two-electron reduction of a relay (Q) and to use the resultant QH2
as a raw material in a separate photocycle under conditions where the
H2-evolving catalyst is localized at the collection point82. The overall
scheme is shown as Fig. 10. Here, water is the source of the O2 and the
reduced relay can be isolated, stored, and used for fuel production as
required. Ideally, the second cycle would reduce CO2 to formic acid83.
This product could be concentrated and used either as a feedstock or as
a source of H2. Quinones are often considered as potential relays but
there has been little genuine progress in effecting this type of coupled
system. Even less is known about how to selectively reduce CO2 to
formic acid84, although its subsequent dissociation into CO2 and H2 is
well known85. We emphasize that such coupled systems represent the
only viable approach to storing sunlight as chemical potential, while
the need to invoke CO2 reduction has become almost as important as
seeking new energy supplies. The absence of any genuinely effective
catalyst for CO2 reduction remains a massive stumbling block. That is
not to imply that strenuous efforts to identify suitable catalysts have
not been made. On the contrary, many different approaches have been
tried, but a genuinely effective catalyst for CO2 reduction remains
elusive86–93.
Molecular self-repair
Perhaps the most intriguing aspect of biological systems is their ability
to induce self-repair. In contrast, virtually no man-made materials
that have a dynamic function possess the ability to sense and repair
the inevitable damage that occurs during operation. Self-repair is an
essential feature of natural photosynthesis; for example, an oxygen-
evolving catalyst is known that can regenerate each 30 minutes
under solar irradiation94 while highly reactive singlet oxygen formed
during side-reactions is consumed by carotenoids95. The idea that an
artificial analog built from organic molecules and maintained under
 Artificial photosynthesis REVIEW

Fig. 10 Simplified representation of a two-color photosystem for solar energy conversion using a relay. S refers to a sensitizer, which might differ for each reaction,
whose purpose is to absorb photons and initiate the necessary redox chemistry. Suitable catalysts are mandatory.

illumination in aerobic conditions can operate without self-protection Closing remarks

is foolhardy. No amount of engineering will overcome this problem
and it is crucial that practical photosystems are equipped with some
kind of built-in protection against photochemical damage. This aspect
of artificial photosynthesis is still in its infancy but four possible
mechanisms can be identified: redundancy, reservoir effects, excision
and replacement, and on-site repair. One such strategy is exemplified
in Fig. 11, where two of the blue porphyrin arms are redundant during
a complete photon cycle96. If one, or even two arms, became damaged
over time the system will not necessarily shut down. Providing a
repair mechanism could be put in place, the array would eventually
re-establish its full working capacity. The ability to create intelligent
artificial repair enzymes is of course a major challenge.
Solar panels on the roof, charging a battery in the basement, are
becoming commonplace. Cars powered by the electrolysis of water
no longer reside solely in the world of fiction. What price power
stations harnessing sunlight and turning out designer fuels for the
chemical industry using water as the sole source of electrons? The
photofixation of CO2, once an esoteric research dream, is now a
necessity, to be utilized to create organic molecules as substitutes
for fossil fuels. We have to develop new catalysts to drive these
reactions under mild conditions and to integrate fundamental
principles of light-induced electron transfer into ordered arrays
where individual molecules act cooperatively on a large scale.
The challenge is immense but so too is the reward. Complacency

(a) (b)

(c)

Fig. 11 Illustration of artificial self-repair processes, including (a) redundancy, (b) the reservoir effect, and (c) inclusion of a bridge that could be cut out and
replaced by selective chemistry at the connections. In each case, illumination of the donor results in through-bond electron transfer to the acceptor but occurs only
if the linkage is intact.

DECEMBER 2008 | VOLUME 11 | NUMBER 12 33

REVIEW Artificial photosynthesis
engulfs us as we talk endlessly about progress made to date in terms
of efficiencies of light-to-electricity conversion. The simple reality
is that little real progress has been made in artificial photosynthesis
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