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Volume 47 | Number 2 | 2011

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www.rsc.org/chemcomm Volume 47 | Number 2 | 14 January 2011 | Pages 581–816
Published on 18 October 2010 on http://pubs.rsc.org | doi:10.1039/C0CC02687E
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ISSN 1359-7345
Pages 581–816
www.rsc.org/members FEATURE ARTICLE

Registered Charity Number 207890
Ziessel and Harriman
Artificial light-harvesting antennae:
electronic energy transfer by way of
molecular funnels 1359-7345(2011)47:2;1-E
FEATURE ARTICLE www.rsc.org/chemcomm | ChemComm
Artificial light-harvesting antennae: electronic energy transfer by way of

molecular funnels
Raymond Ziessel*a and Anthony Harrimanb
Received 20th July 2010, Accepted 17th September 2010
DOI: 10.1039/c0cc02687e
Electronic energy transfer (EET) plays a critical role in many biological processes and is used
by nature to direct energy to a site where chemical reactions need to be initiated. Such EET can
occur over large distances and can involve many individual molecules of identical, similar or
disparate chemical identity. Advances in spectroscopy and data processing have allowed the rates
of EET to be measured on extremely fast timescales such that improved mechanistic insight
becomes feasible. At the same time, highly sophisticated synthetic operations have been devised
that facilitate the isolation and purification of elaborate multi-component molecular arrays. A key
feature of these arrays concerns the logical positioning of individual units in a way that favours
directed EET along the molecular axis or along some other preferred pathway. The availability of
these novel molecular materials allows close examination of popular theoretical models and paves
the way for the development of advanced molecular sensors, artificial light harvesters, fluorescent
labels and sensitizers. Of particular interest is the spectacular growth in the application of boron
dipyrromethene dyes as basic reagents in such artificial photon collectors and these compounds
have dominated the market in recent years because of their synthetic versatility and valuable
photophysical properties. In this article, recent developments in the field are highlighted in terms
of synthesis and subsequent spectroscopic exploration.
Introduction
a
Laboratoire de Chimie Organique et Spectroscopies Avanceés
(LCOSA), Ecole Européenne de Chimie, Polyme`res et Mate´riaux,
Once again the attention of mankind has turned towards the
Universite´ de Strasbourg, 25 rue Becquerel, 67087 Strasbourg Cedex urgent need to identify and harness supplies of renewable
02, France. E-mail: ziessel@inistra.fr; Web: http://www-lmspc. energy and, in particular, the concept of artificial photosynthesis
u-strasbg.fr/lcosa; Fax: 33 3 6885 2761; Tel: 33 3 6885 222 2689 has entered the popular vocabulary.1 In essence, this means
b
Molecular Photonics Laboratory, School of Chemistry,
Bedson Building, Newcastle University, Newcastle upon Tyne, that we must develop viable molecular systems able to store
UK NE1 7RU. E-mail: anthony.harriman@ncl.ac.uk sunlight in the form of chemical or electrochemical potential.
Doctor Raymond Ziessel Professor Anthony Harriman

gained a PhD in organic spent fourteen years at the
Chemistry from the University Royal Institution, working on
Louis Pasteur of Strasbourg the fundamental issues relating
under the guidance of Professor to artificial photosynthesis in
Jean-Marie Lehn and Doctor collaboration with Lord George
Jean-Pierre Sauvage. He is Porter. This work was recog-
presently the Director of nised by the award of the
the Laboratoire de Chimie Corday-Morgan Medal (RSC)
Organique et Spectroscopies in 1984 and Le Prix Gramma-
Avanceés (LCOSA) located ticakis-Neumann Prize en
at the Engineer School of Photochimie by the European
Chemistry (ECPM) in Photochemistry Society in
Strasbourg. Recent research 1985. He moved to the Univer-
Raymond Ziessel interests have focused on the Anthony Harriman sity of Texas at Austin in 1988
preparation of novel liquid to become Director of the
crystals and organogelators, metallo-polyacetylenes and lanthanide Center for Fast Kinetics Research before moving to the Univer-
complexes for biomaterial labeling and time-resolved fluores- sity of Newcastle in October 1999. Research at Newcastle has
cence imaging. He has published over 440 papers in Inter- been concerned with various aspects of light-induced energy and
national Journals and monographs, is co-author of 13 PCT electron transfer in multi-component molecular systems and has
patents, and has given 270 research lectures, in over 15 countries involved several long-standing international collaborations.
worldwide. He is the recipient of the Silver Medal CNRS award More than 360 publications have appeared in peer-reviewed
in 2000. journals and more than a hundred talks have been given at
international conferences.
This journal is c The Royal Society of Chemistry 2011 Chem. Commun., 2011, 47, 611–631 611
Such generic ideas are far from new and reappear each that of the various models of light-harvesting systems
20 years or so. One aspect of artificial photosynthesis which proposed over the last few decades.4,14 The general operating
has been around since the early 1970s relates to the principle of principle of these systems involves collecting photonic energy
trying to mimic some of the more essential features of the at all wavelengths below a certain threshold value and then
natural process, leading to the development of bio-inspired transferring that excitation energy over a vast collection of
materials.2 Paramount among the multifarious steps associated individual pigments. The first step involves a cascade effect in
with natural photosynthesis is the collection of sunlight by which excitation energy is transferred between dissimilar
light-harvesting complexes (LHCs) and the subsequent trans- pigments, each process being driven by a thermodynamic
port of the absorbed photons around a large network of factor that loses excess energy in the longest wavelength
well-defined topology.3,4 This excitation energy is shuttled absorber. It is not excluded that some of these relay dyes
around the network until trapped at a reaction centre complex absorb energy to a higher excited state or vibrational level.
where it is used to initiate a charge-separation step.5 The Subsequently, energy migration takes place whereby the
resultant electrochemical energy is converted into chemical excitation energy moves incoherently around the array until
potential and stored in the form of carbohydrates and other reaching the final acceptor. Each step in the overall reaction is
valuable substances. Later, by way of a complex series of dark fast, often ultrafast, so that a large distance is covered in a
reactions, the accumulated sugars are oxidized in chemical short space of time.15 This type of behaviour is essential for the
processes so as to produce localised energy that can be LHC to compete with the effects of fluorescence and/or non-
adapted and used by the living organism. The machinery used radiative decay of the excited state. The sheer speed of the
to operate the reaction centre complex is based on the precise process also serves to by-pass triplet formation and thereby
positioning of a series of redox co-factors able to create a helps to protect the system against oxidative stress.
gradient of electrochemical energy that spans the membrane It should be emphasized that in natural LHCs the pigments
and leads to long-range charge separation.6 As the result of are arranged in extremely well-designed and precise networks
protein engineering modified and amended over some billions that act in a cooperative fashion. For example, the LHC of the
of years, the primary pigments inherent to the reaction centre purple bacterium rhodopseudomonas acidophile16 arranges the
complex do not themselves function as large-scale photon pigments into rings of discrete size, with individual molecules
collectors but leave this function to the LHCs.7 This arrange- being held in place by the protein scaffold. This realisation has
ment ensures that the dark reactions of photosynthesis are not led to tremendous effort being devoted to the synthesis of
severely limited by the rate of light absorption at low photon wheel-like porphyrin arrays.17 The availability of high-quality
flux.8 Furthermore, the special demands built into photon crystal structures of natural LHCs has also facilitated
harvesting and charge separation can be optimised separately comprehensive studies into the mechanisms by which rapid
and over disparate evolutionary timescales. In this review, we electronic energy transfer (EET) takes place. A great amount
focus on the construction of artificial LHCs using unnatural is known now about both natural LHCs and the theory of
but bio-inspired reagents. EET so that, in principle, it should be possible to construct
The largest natural light-absorbing antennae are found in effective artificial analogues based on the cascade effect. Such
dedicated green bacteria (i.e., chlorobiaceae), which contain materials could be used as organic solar concentrators,
from 1000 to 2000 bacteriochlorophyll molecules per reaction sensitisers for solar cells, unnatural neural networks, opto-
centre complex.9 In purple bacteria, the number of absorbing electronic components or advanced signalling devices. The
pigment molecules per reaction centre varies from 50 to critical requisite is the ability to position reagents at the correct
250 depending on the organism and environment.10 In higher location in logically designed networks. Ideally, the main
plants, there are 200 or more chlorophyll-based antennae for synthetic motif should involve supramolecular construction,
each reaction centre.11 A remarkable feature of all such but this is beyond our current capability.
natural LHCs is that very few of the photons absorbed by There are many reviews dedicated to the design of linear and
the chromophores are lost at low photon density and so the cyclic porphyrin arrays as artificial models for photosynthetic
reaction centres are supplied with a constant source of photons events.4a,18 Here we focus on the design and synthesis of
of appropriate energy.12 At high photon density, the system artificial LHCs based on non-porphyrinic chromophores. In
switches on special processes to deal with the overload and to particular, we draw attention to the virtues of boron dipyrro-
protect the organism from the consequences of adventitious methene (Bodipy) dyes as reagents with which to construct
production of highly-reactive radicals. This type of inherent next-generation solar concentrators. Such compounds have
self-defense mechanism becomes an important feature of been attached to a wide variety of ancillary fluorophores so as
artificial arrays if the latter are to survive the harsh conditions to facilitate directed EET processes in which the Bodipy
associated with aerobic illumination. functions as donor, acceptor or relay. Before doing so, we
A particularly high level of sophistication is reached with will briefly review selected EET events in related systems.
cyanobacteria and red algae which contain an assembly of
antennae known as phycobilisomes.13 This supramolecular Multiple EET processes occurring in supramolecular
particle is so well constructed that a single photon absorbed
systems
anywhere within the structure is transferred to the few terminal
acceptors in a unidirectional manner and in five to six kineti- As mentioned above, the light-harvesting machinery of the
cally significant steps.5 Remarkably, little energy is lost in the phycobilisomes present in certain algae and marine bacteria is
process and the elaboration of the actual design transcends a near-perfect illustration of multiple EET events leading to
612 Chem. Commun., 2011, 47, 611–631 This journal is c The Royal Society of Chemistry 2011
the concentration of photonic energy at a preferred site. A key portion of the sensing system consists of MBP modified with a
feature of these natural systems relates to the use of a protein long-wavelength absorbing cyanine (e.g., Cy3 or Cy3.5 for
matrix to assemble the various components into ordered arrays cyanine-3-monofunctional or cyanine-3,5-difunctional dyes)
in such a way that some kind of self diagnosis and repair as can be seen from Fig. 2a. The acceptor portion of the
becomes possible. Recognising the severe difficulties associated sensor consists of a b-cyclodextrin (b-CD) modified with either
with trying to duplicate the sophistication of photosynthetic the fluorescent cyanine Cy5 or the dark quencher QSY9.
systems, it has proved possible to mimic certain features at least Binding of the modified b-CD to the dye-conjugated MBP
in a crude manner. One such example makes use of well-defined results in the self-assembly of the EET complex and leads to an
biological structures to carefully position unnatural reagents,19 output signal at 669 nm (Fig. 2b).24
this situation being the opposite of the normal approach in Added maltose displaces the b-CD adduct and thereby
which the rate of EET is used to elucidate complex biological disrupts the complex, resulting in the appearance of the
structures.20 Deoxyribonucleic acid (DNA) has been used characteristic donor fluorescence at 596 nm. When b-CD
extensively as a scaffold for a variety of chromophores due to pre-loaded with a dark quencher is employed, the system
its ability to anchor dyes at discrete sites along the backbone displays a remarkable OFF/ON switching process. A different
and to hybridise multiple dye-labelled oligonucleotides to a format uses the Cy3-MBP conjugate as a relay between a
complementary strand.21 The main advantage of using DNA as quantum dot (QD) and the Cy3.5-labeled analogue of maltose
a vehicle by which to assemble donor/acceptor pairs able to linked to the central binding pocket of MBP (Fig. 2c).
drive EET events stems from the ability to predict and control Although maltose sensing in this QD-MBP displacement
to some extent the mutual orientation of the attached sensor is based on changes in the ratio of emission from
reagents.22 In the case of flexible linkers the orientation is MBP-Cy3 and Cy3.5, the sensor is driven by the QD since
uncertain. A fine example of multi-labelled DNA encoding this is the primary chromophore at 530 nm (Fig. 2c).25
FAM (i.e., 6-carboxyfluorescein, lem at 525 nm), TAM Each of these examples of EET in supramolecular systems is
(i.e., N,N,N 0 ,N 0 -tetramethyl-6-carboxyrhodamine, lem at made possible by the well-defined features of through-space
585 nm) and Cy5 (i.e., cyanine-5 monofunctional dye, lem at energy transfer. In covalently attached donor/acceptor pairs,
670 nm) fluorophores spaced by various lengths of 1 0 ,2 0 -dideoxy- the situation might be more complicated in that through-bond
ribose phosphate chains has been used in combinatorial electron-exchange interactions become possible. The two
fluorescent EET tags for multiplex biological assays (Fig. 1).23
Different fluorescence emission signatures (lem) can be obtained
from a single excitation wavelength and by altering the number
of sugar phosphates interposed between the three fluorophores.
By virtue of changing the spacer, the emission can be tuned so
that unique ratiometric signatures are produced. Eight such tags,
each bearing a unique fluorescence signal, have been engineered
from three different dyes. Furthermore, genotyping assays using
three-colour capillary array electrophoresis allow multiplex
detection of six nucleotide polymorphisms.23
Maltose binding protein (MBP) has been used to probe
various protein-based multi-EET configurations. The donor
Fig. 1 Molecular structure of the CFET tags adapted from ref. 23. Fig. 2 (a) Molecular structures of Cy3.5 and QSY9. (b) Schematic
The linkage between the fluorophores and the thymidine moieties representation of the EET-based sensing scheme adapted from ref. 22.
is a six-methylene chain while DNA can be linked in place of the (c) A double EET-based system uses a quantum dot (QD) as energy
oligonucleotide sequence. input as reported in ref. 25.
permit the facile introduction of disparate functionalities at
the periphery of the dipyrrin core, including the meso position,
and at the boron atom. The robust character of Bodipy dyes
also facilitates post-functionalisation and allows the isolation
of entire libraries of tailored dyes.30 The range can be further
extended using combinatorial techniques based on the
so-called ‘‘click’’ chemistry. Such protracted synthetic
strategies are fully justified by the enormous variety of appli-
cations found for Bodipy derivatives, spanning from sensing
materials, fluorescent probes, laser dyes and two-photon
absorbers to soft matter (e.g., liquid crystals, organo-gelators,

polymers) and electroluminescent devices (e.g., OLEDs and
solar cells).31,32
A common problem found for organic fluorophores, or
more generally for any singlet emitter, is the small gap between
the excitation and emission wavelengths (i.e., the Stokes’
shift). A small Stokes’ shift leads to severe problems with

achieving adequate resolution in fluorescence microscopy and
can cause significant loss of emission intensity. To help
overcome this difficulty, multi-component dyes have been
introduced that operate by way of intramolecular EET.33
Conceptually, such systems are engineered from a donor–
spacer–acceptor (D–Sp–A) dyad where the terminal emitters
are linked by a non-emissive spacer in such a way that the
donor can be illuminated with high selectivity. Provided the
energetics are balanced appropriately, EET occurs from donor
to acceptor, with the latter fluorescing at much longer wave-
length. Such simple molecular systems are often termed EET
cassettes.34 The challenge at the onset was to circumvent the
inherent limitations of the classical fluorescein–rhodamine
Fig. 3 Electronic energy transfer cassettes based on various Bodipy systems (e.g., poor optical resolution, limited photochemical
dyes as adapted from ref. 32. stability, pH dependence, gel mobility shifts, etc.) by using
functionalised Bodipy dyes. The original systems are sketched
mechanisms, often referred to as Förster (or coulombic) and in Fig. 3 and start from the alkyne derivatives of the emissive
Dexter processes, exhibit quite different rate vs. distance dyes, which are subsequently cross-linked using a palladium
dependences (see later) and distinguishing between the two catalyst. The first step involves a statistical reaction that
mechanisms can be hazardous, especially at intermediate provides the target compounds in reasonable yield.32
separation distances. Before expanding on this point we It should be noted that dyads 2 and 3 possess a functional
illustrate some of the more recent research conducted with group for attaching the dye to a substrate but insolubility in
Bodipy-based EET events. aqueous media severely limits the range of potential applica-
tions. In each case, the overall efficiency of EET from the
donor to the acceptor is about 95%. The pseudo-Stokes’ shifts
EET involving simple Bodipy dyes
vary between 1450 and 4500 cm1 while the fluorescence
It is clear that multiplexing experiments of the type summarised quantum yields recorded for the terminal acceptors range
above can be used to extract a considerable amount of from 12 to 60% (Fig. 3). Steric crowding prevents compounds
information about the local environment simply by registering 1–3 from adopting a fully planar geometry. As a consequence,
the emission profile with a suitable database compiled for absorption spectra measured for these cassettes resemble
the same excitation wavelength.21,26,27 This kind of strategy linear combinations of the spectra of the individual moieties.
demands that the dyes possess narrow but intense absorption From this viewpoint, these materials can be considered to act
and fluorescence spectral profiles, with minimal overlap, and like independent modules linked to a preorganized platform.
high emission quantum yields. Amongst the most popular dyes Interestingly, direct attachment of an anthracene module to
fluorescein, rhodamine, pyrene, perylene, rylene, perylene Bodipy via a Suzuki coupling reaction also provides a cassette
diimide, flexible cyanines (Alexa), and rigid cyanines such as (namely compound 4 in Fig. 4) for which a twisted conforma-
4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (F-Bodipy) have tion minimises conjugation between the subunits.35 This holds
been studied extensively.28 The upsurge of interest in the latter true also for the Bodipy-anthracenyl dyad, 5, prepared by
Bodipy dyes stems from their pronounced stability, high Sonogashira cross-coupling.
absorption coefficients, narrow emission profiles and fluores- The situation is somewhat different for compounds 6 and 7
cence quantum yields that approach unity in many cases.29 since modest electronic communication between the terminals
Furthermore, well-established protocols are available that is evident from cyclic voltammetry studies. These compounds
Fig. 4 Examples of anthracene-linked Bodipy dyes as adapted from

ref. 35.
are not cassettes in the strict sense of the definition because the
conjugated p-systems are not subjected to internal twisting.
This situation is reflected by the fact that the absorption
maxima are red-shifted and broader than those observed for
compounds 4 and 5. Near complete EET is observed from the
donor (anthracene) to the acceptor (Bodipy). Indeed, the
quantum yields for Bodipy-type fluorescence are independent
of excitation wavelength across the entire spectral window.
The virtual Stokes’ shifts are quite large, varying from 10 300 cm1 Fig. 6 Synthetic protocol used to prepare Bodipy dyes bearing
polyaromatic moieties linked to the boron centre.
for 4 to about 8000 cm1 for the other compounds.29
Pyrene building blocks have been used to construct cassettes
by direct condensation with pyrenecarbaldehyde (compound 8) 7400 cm1 for 9, and 3700 cm1 for 10). The rate of EET
or by linkage via alkyne tethers at the Bodipy meso position depends on the structure of the dual-dye system and decreases
(Fig. 5). Compound 9 was prepared by a single cross-coupling as the centre-to-centre separation distance increases. The EET
reaction promoted by Pd(0), whereas synthesis of dye 10 efficiency, however, exceeds 90% in all cases. Linking two
required a multi-step procedure based on a succession of pyrene residues together via an ethynylene spacer leads to a fall
cross-coupling and deprotection steps.36 in the EET efficiency, with the two polycycles acting as a single
Very efficient intramolecular EET from pyrene to Bodipy chromophore.
takes place via the Förster dipole–dipole mechanism, providing A convenient tool by which to connect polyaryl residues to
for large ‘‘virtual’’ Stokes’ shifts (e.g., 10 900 cm1 for 8, Bodipy dyes is to replace the fluorine atoms with aryl or
alkynylaryl modules. An organometallic approach (i.e., organo-
lithium or Grignard reagents) was used as the method of
choice for effecting these replacement reactions. Such routes
have provided access to a library of stable C-Bodipy and
E-Bodipy dyes and opened the way to the preparation of
new dyads and cascade-type arrays (Fig. 6).37 This work has
been extended to cover cases where the alkynylaryl derivative
is not available or lacks sufficient stability. This protocol is
based on initial replacement of the fluorine atoms with protected
alkynyl functions, followed by deprotection and palladium(0)
catalysed cross-coupling. This situation is illustrated for
the synthesis of dye 19, which occurs in excellent yield.38
Interestingly, in all cases, excitation into the polyaromatic
residue results in strong emission from the Bodipy nucleus
with very little residual fluorescence from the donor. Intra-
molecular EET is quantitative when there is pronounced
Fig. 5 Synthetic protocol used to prepare some pyrene-linked Bodipy spectral overlap between fluorescence from the arene and
dyes. absorption by Bodipy. In many cases, the relevant absorption
band corresponds to an upper-lying excited state resident on not been necessary to invoke the Dexter mechanism in this
the Bodipy nucleus, which is typically found in the region particular case.
370 to 440 nm.39,40 It is interesting to consider the possibility of setting up a
Related hybrid dyes can be obtained simply by carrying cascade effect in the asymmetric derivative 24. Here, photons
out the synthesis in the presence of two different Grignard absorbed by the pyrene unit can be transferred directly to the
reagents. The resultant mixture is easily separated by column Bodipy S2 state, or to the perylene unit. The latter is perfectly
chromatography to give the individual dyes (Fig. 7).41 This is placed to act as an energy acceptor. The Förster-type overlap
an interesting situation because it allows the isolation of dyes integral is high, the centre-to-centre separation distance is
possessing strong absorption bands at predetermined wave- modest, and the mean orientation factor is reasonable. Model
lengths, suitable for excitation with laser diodes, or covering calculations using reference compounds predict that the rate of
an unusually broad spectral envelope. In the latter case, most Förster-type EET from pyrene to perylene in 24 is on the order
of the absorption peaks can be assigned to a particular of 5 1010 s1. As such, we might expect photons absorbed by
chromophore. the pyrene unit to be channeled to perylene or Bodipy units
The optical and photophysical properties of C-Bodipy dyes with (roughly) equal probability.
(prototypic examples are 12 and 13) depend on the size of the One area of intense current research activity is the develop-
aryl residues and on the nature of the surrounding solvent. A ment of dyes that absorb in the 650 to 900 nm window in order
solvatophobic effect in which the aryl substituent seeks to foresee potential applications in biomedical analyses for
to minimise surface contact with certain types of solvent which the absorption of haemoglobin in blood and auto-
molecules causes slight buckling of the dipyrrin framework.40 fluorescence by biological residues such as tryptophan are
This latter effect is not observed for the classical F-Bodipy dye minimal.44 As a first step towards the development of dyes
11, whose spectroscopic properties are essentially insensitive to emitting in the far-red or near-IR and displaying large Stokes’
changes in solvent polarity. Note that for some 3,5-disubstituted shifts, a tandem technology has been developed that leads to
F-Bodipy dyes, the so-called distyryl dyes, red shifts are the formation of bis-indolomethene dyes (Fig. 8).45 Here the
observed on increasing the polarizability of the solvent.42 synthesis is straightforward and provides access to blue-green
Extremely fast intramolecular EET from a polycycle to the absorbing dyes on relatively large scales. Remarkably, the
Bodipy residue occurs for dyes 22 to 24 while, in contrast to fluorescence quantum yields remain high, even for dyes
the case considered for the corresponding F-Bodipy dyes, the emitting above 700 nm. Further development of these dyes
boron-ethynyl substituents in these E-Bodipy dyes do not has resulted in highly efficient cascade-type EET from attached
affect the photophysical properties of the Bodipy unit. There pyrene residues to the bis-indolomethene fragment, leading to
are no obvious indications for competing intramolecular Stokes’ shifts as high as 12 780, 13 760 and 11 475 cm1,
electron transfer, despite the modest thermodynamic driving respectively, for compounds 25, 26 and 27. Also for these
forces for certain processes. It is possible that the weak solvent unusual dyes intramolecular EET from pyrene to the second-
polarity, relatively long through-space distances, and/or poor excited singlet state of the Bodipy subunit appears to be
conductivity of the B atom inhibit electron transfer and quantitative and consistent with the Förster dipole–dipole
thereby favour EET. The ethynyl substituent merely functions mechanism.45
as an ancillary light harvester for near-UV photons. In this
respect, the asymmetric derivative 24 is the most attractive Bodipy as an energy donor
dye, since it collects photons across most of the accessible
spectral range. It also provides for a large ‘‘virtual’’ Stokes’ The all-important antenna effect observed with polyaromatic
shift of about 11 000 cm1. Intramolecular EET appears to be units as ancillary light harvesters has been extended to include
consistent with the Förster dipole–dipole mechanism, at least the use of Bodipy as the primary photon collector, rather than
for the perylene-based chromophore. It is possible, however,
that the rate of EET is augmented by Dexter-type through-
bond interactions, given the short separation and conjugated
ethynylene linker. The latter is known to be an effective bridge
for electron-exchange processes.43 The effectiveness with
which an electron can tunnel across the central boron atom
has not been explored to any great effect but nonetheless it has
Fig. 7 Examples of mixed Bodipy dyes bearing polyaryl dyes attached Fig. 8 Examples of blue–green absorbing Bodipy-based dyes
via the boron atom. equipped with a pyrene residue as the input energy donor.
Fig. 10 Examples of a molecular triad and tetrad comprising,

respectively, two krypto-Bodipy dyes (lem at 540 nm) linked
to a distyryl framework and three krypto-Bodipy residues connected
Fig. 9 Example of a molecular triad composed of two Krypto-Bodipy to a central distyryl Bodipy fragment (labs at 650 nm) as adapted
residues (lem at 540 nm) and a single green absorber (labs at 700 nm). from ref. 48.
using this residue acting as the terminal acceptor. A con- way that cascade EET is favoured and extremely fast; (iii) the
venient strategy by which to link together disparate chromo- local topology and nature of the connecting units must
phores involves attachment of ethynyliodophenyl derivatives promote this energy transfer either by the Förster dipole–
at the boron atom since this approach facilitates post- dipole mechanism (i.e., through space favoured by good
functionalization (e.g., 28 in Fig. 9). The latter material is a spectral overlap) or by the Dexter double electron-exchange
green absorbing dye that can be linked easily to Bodipy mechanism (i.e., through bond promoted by orbital overlap);
subunits that themselves absorb at higher energy. The result (iv) both spacer and selected dyes must be chemically and
is a new type of cascade molecule that emits at relatively long photochemically stable, thereby avoiding photobleaching
wavelength. For example with triad 29, EET from the and destruction of the scaffold; and finally (v) the synthetic
krypto-Bodipy (which is prepared from dimethylethylpyrrole) chemistry should be versatile, efficient, and sufficiently
to the central bis-indolodipyrromethene occurs with an selective to ensure the absence of interactive impurities. One
efficiency of around 95%. In this particular case, the experi- of the earliest examples of a multi-component cluster was
mental rate constant is in quite good agreement with that assembled stepwise by linking four disparate chromophores in
calculated using Förster theory. However, it should be stressed a controlled manner. This logical arrangement favours
that related dual-chromophore dyes composed of F-Bodipy efficient photon collection and migration to a terminal Bodipy
dyes are known to undergo fast through-bond energy transfer.46 acceptor (Fig. 11).51
As such the mechanism for EET in these dyads appears to The primary energy acceptor for the cluster is a krypto-
depend on several critical features. A further point of interest Bodipy, which emits at 540 nm, and different polyaromatic
with these dyes is that the lowest-energy triplet state does not modules have been substituted in place of the regular fluorine
sensitise formation of singlet molecular oxygen. This situation atoms at the boron centre. This approach ensures that minimal
aids the photo-stability of the dye in solution.47 spectroscopic perturbations will occur and that each absorber
Absorption spectral profiles recorded for compounds 30 maintains a discrete spectroscopic integrity. The synthetic
and 31 (Fig. 10) closely resemble linear combinations of those protocol was inspired by previous post-functionalization
recorded for the individual modules. Rather weak electronic strategies carried out on Bodipy subunits.30,31 The crucial step
communication between the subunits is imposed on the is the statistical attachment of the disubstituted-pyrene module
near orthogonality of each Bodipy unit by the two methyl Py, which requires careful optimisation and specific conditions.52
substituents in the 1,7-positions. Energy transfer from the A sequence of cross-coupling reactions using palladium(0)
peripheral dyes to the central distyryl dye reaches about promoted chemistry and subsequent alkyne deprotection
72% in both these multi-chromophoric materials.48 allows routine access to the sophisticated dye BPePyF in a
minimum of synthetic steps. This particular dye was designed
to absorb light across the range from 200 to 550 nm. The
Cascade EET in Bodipy-based clusters perylene unit linked to boron via a 1,4-diethynylphenyl
fragment collects photons in the 320–490 nm, while the pyrene
V-shaped systems
dye joined to the same boron atom absorbs strongly in the
The optimisation of photon collectors for use in artificial 280–420 nm wavelength window. The ethynylfluorene moiety
photosynthetic devices aimed at converting sunlight into absorbs in the UV below 300 nm.
chemical potential is a topic of significant interest.14,49,50 To By using a variety of model compounds allowing selective
be viable, such artificial LHCs have to fulfil several require- excitation into each of the individual units it was possible to
ments that take due notice of: (i) the energy distribution of the establish a full picture for the EET cascade in this cluster
solar spectrum, spanning from the UV to the near-IR region; (Fig. 12). Thus, illumination into any of the polycyclic hydro-
(ii) the sequence of chromophores must be chosen in such a carbons results in almost exclusive emission from the Bodipy
EET can occur to either the S1 (i.e., with perylene as donor)
or S2 (i.e., with pyrene as donor) states associated with the
acceptor. There are also serious concerns relating to the
general applicability of Förster theory to calculating EET
rates at such short separations and consequently the validity
of the computed values might be questioned.
This early multi-cascade prototype was extended to the
construction of expanded Bodipy units that absorb and emit
across the far-red region.53 The synthetic strategy used for the
preparation of the new array is illustrated by way of Fig. 13. It
is notable that the various appendages have minimal effect on

the photophysics of the green absorbing dye (S0 - S1; labs =
730 nm), which emits in the far-red region (lem = 752 nm,
FF = 0.19, tS = 6.2 ns). On this basis, the radiative rate
constant for the green-emitting chromophore is calculated as
being 3 107 s1. This value is in reasonable agreement with
that determined (kRAD = 4.4 107 s1) from the Strickler–

Berg expression,54 but is significantly smaller than that found
for conventional Bodipy dyes (kRAD E 1.5 108 s1). In the
Fig. 11 Schematic representation of the stepwise assembly of a multi- main, this disparity can be accounted for in terms of the
component BPePyF dye in which each module (namely E-Bodipy (B), different mean emission wavelengths and molar absorption
3-perylene (Pe), 1,6-pyrene (Py), 2-fluorene (F)) is linked to its partner coefficients.55 The broad S0 - S2 optical transition associated
via an ethynyl or 1,4-diethynylphenyl spacer. with the green-emitting chromophore is located at about
400 nm. It is reassuring to note that essentially all photons
absorbed by the fluorene, pyrene, perylene and diethynyl-
phenyl units are channelled to the green emitter. All the
individual EET steps are fast (Fig. 14) and, unlike the earlier
cluster, the rate of EET from pyrene to the green dye is much
faster than that for EET from perylene to the same acceptor.
This cluster also provides for a large ‘‘virtual’’ Stokes’ shift in
excess of 17 000 cm1.
There is negligible spectral overlap between fluorescence
from the ancillary photon collector and the first-allowed
absorption transition localised on the terminal Bodipy acceptor.
However, pronounced overlap occurs with the S2 absorption
transition of the acceptor and it is clear that EET occurs via
Fig. 12 Schematic representation of sequential EET processes as

calculated from Förster theory for the multi-component compound
BPePyF. Here, kF refers to a static system assuming only dipole–
dipole interactions, while kF* refers to a dynamic system that allows
for multipole–multipole interactions. Note kEET refers to the experi-
mentally determined rate constant for EET.
subunit. The rates of intramolecular EET were determined

from time-correlated, single-photon counting studies and
compared with the rates for coulombic interactions computed
from the Förster expression (Fig. 12). It has been possible to
measure rate constants for two of the key steps, although
transfer from fluorene to pyrene is too fast to be determined.
Indeed, it is difficult to decide if the fluorene and pyrene
fragments combine to form a single giant chromophore or
retain some degree of individual electronic character. Also, the
EET processes doubtless contain some important contribution
from the through-bond mechanism. This latter process can be Fig. 13 Schematic representation of the stepwise synthesis of the
termed ‘‘bridge-mediated EET’’ and might be the dominant multi-component GPePyF dye in which each module (namely,
route for intramolecular EET in some cases. Part of the E-Bodipy (GPh), 3-perylene (Pe), 1,6-pyrene (Py) and 2-fluorene (F))
problem here, at a mechanistic level, relates to the fact that is linked to its partner via an ethynyl or 1,4-diethynylphenyl spacer.
Fig. 14 Presentation of the rate constants for intramolecular EET

occurring in the multi-component GPePyF compound as derived by
experiment.
the upper-lying excited state. Not much is known about the S2

state of Bodipy dyes but it has been shown that internal
conversion from S2 - S1 is extremely fast (i.e., 100–250 fs)
in conventional Bodipy-based dyes.56 The expanded (i.e.,
green) Bodipy residue shows more pronounced S0 - S2
absorption than does the conventional (i.e., yellow) Bodipy
chromophore and thereby enhances the rate of EET from a
given donor. Although there are several examples of EET
from the S2 level of the donor,57,58 direct involvement of the S2
state on the acceptor is scarce.59 Such an effect takes on added Fig. 15 Molecular formulae for selected donor–acceptor type
significance when designing improved solar concentrators dendrimers as adapted from ref. 62: (a) reaction pathway; (b) size of
intended to harvest an unusually large fraction of incident the dendritic units.
sunlight. Indeed, the way is now open to maximise the collec-
tion efficiency by adding a further layer of dyes that absorb at In the specific case of the above-referenced dendrimers,
lower energy and transfer directly to the S1 state of a green- the energy donor is located at the periphery of the core.
emitting acceptor (vide infra). Selective excitation of this molecule (labs E 550–650 nm;
lem E 620–750 nm) results in highly efficient energy transfer
(>90%) to the central aza-Bodipy acceptor (labs E 600–750 nm).
Dendrimer-like systems The pronounced spectral overlap between emission from the
Near-IR absorbing dyes usually comprise highly extended mono-styryl Bodipy and absorption by the green aza-Bodipy
p-conjugated electronic systems that impose planarity and is in favour of a resonance type of energy transfer. It should
rigidity on the molecular framework. In turn, such structural also be noted that the escalation in molecular size on going
facets tend to promote spectral broadening and self-aggregation from G0 to G3 is matched by a substantial increase in
in solution. In addition, highly delocalised p-systems are often fluorescence quantum yield (FF) from 0.21 to 0.66 whereas
susceptible to photochemical damage initiated by attack from the unsubstituted green core has a fluorescence quantum yield
singlet molecular oxygen, leading to photobleaching. There is of only 0.16.62 Many other dendrimer-style architectures are
the added problem that it is difficult to concentrate these types possible and, in some cases, have been realised with related
of molecules into small volumes, as is needed to construct an organic and organo-metallic dyes. An interesting feature of
effective LHC, without running into difficulties from self- such systems is the fact that the redox chemistry of the central
quenching of the excited states and/or solvatophobic inter- unit changes as the number of layers increases due to its
actions. A potential way around the problem is to design general inaccessibility and screening by surrounding chromo-
dendrimers that incorporate discrete chromophores in the phores. Such behaviour does not affect the rates of EET but
form of layers.60,61 In particular, there now exists a battery of does perturb the rates of light-induced electron transfer. This
chemical tools that can be used to prepare stable dyes bearing effect allows tuning of the processes in favour of EET.
one or more terminal alkyne functions that themselves are
Circular systems
suitable for subsequent ‘‘click chemistry’’. Such approaches
permit the synthesis of dendrimers containing several layers of Nowadays the chemistry of Bodipy has reached such a high
dyes able to undergo EET processes that essentially focus the level of sophistication that the absorption and emission
photonic energy at the innermost chromophore or at the spectral properties can be modified at will via, for instance,
periphery. Examples such as 34–36 have been prepared along extending the degree of p-electron delocalization of the
these lines (Fig. 15).62 indacene core by virtue of importing unsaturated groups to
molecular-scale photoactive wires.64 The primary purpose of
such materials is to replace conventional metallic wires with
molecular analogues able to transfer information along the
respective molecular axis, often under the influence of photonic
or electrical stimulation. In seeking to design improved photonic
wires, many rigid oligomers have been prepared, often being
constructed around chelating fragments (e.g., bipyridine,
phenanthroline, terpyridine, . . .) suitable for coordination of
phosphorescent transition metal (e.g., Ru, Os, Pt, Ir) centres.65
One of the most stable, versatile and adaptable organic
fragments identified as a building block for such wires is the

1,4-diethynylphenyl module. Indeed, a variety of elegant and
well-characterised p-conjugated architectures have been con-
structed utilising the power of alkyne chemistry and applied to
Fig. 16 Star-shaped arrays constructed with Bodipy dyes grafted such functions. At the extreme, conductive polymers have also
onto a truxene core. The chemistry exemplified here allows prepara- been prepared along the same lines.66 More recently, these
tion of a variety of mixed compounds (TAB2, TA2C, TB2C, TBC2,

approaches have been used in conjunction with Bodipy-based
TA2B, . . .) which are useful models by which to better understand the
dyes in an attempt to engineer photonic wires of nanometric
EET pathways.
dimensions. For example, rigid systems have been prepared
using compounds 38–41 and the technology adapted to
the 3,5-positions.30,31 In this way, blue- and green-absorbing
functionalise organic dyes.67,68 This is nicely illustrated by
dyes can be prepared routinely on a large scale and in pure
way of Fig. 17 where a convergent series of oligomers has been
form. The range of available dyes is further expanded by
synthesized via a cycle of reactions notably including statistical
attaching strong electron-donating groups, such as dimethyl-
Sonogashira coupling and deprotection steps.
amino, at the 4-phenyl positions of the added styryl fragments.
Linking these dyes in a linear fashion serves to shift the
We can illustrate this type of approach by reference to the
absorption maximum to the red by ca. 90 nm as a consequence
tripodal truxcene platform. Here, three different dyes have
of the increased p-electron conjugation running along the
been appended to a single scaffold in order to generate a
2,6-axis of the Bodipy core.69 Also, of some interest is the
directional EET cascade.63 The truxcene platform, which is
increased molar absorption coefficient, which now reaches
fluorescent under UV illumination, is flat and possesses C3
routinely as high as 250 000 M1 cm1. A further feature of
symmetry. The resultant tri-chromophoric assembly is readily
this extended conjugation is that there are no clear absorp-
soluble in organic dyes and operates as a reasonably effective
tion maxima for individual modules but instead the spectrum
artificial LHC (Fig. 16).
shows a broad absorption envelope stretching over an
In the assembled superstructures, fluorescence from the
inordinately wide range. By illumination on the blue edge of
truxcene scaffold is absent when one or more Bodipy dyes
the main absorption band, intense fluorescence can be observed
are in place. Excitation spectra support the notion of rapid
at 620 nm (FF = 0.58) for compound 41, where n = 3, and
EET from the scaffold to the Bodipy dye, a process favoured
by the strong spectral overlap integral. Now, in the specific
case of TABC the fluorescence spectral profile is dominated
by emission characteristic of C, which appears at 767 nm,
indicating that the excited states of A, B and the truxene core
are efficiently quenched by the lower-energy absorbing subunit
C. Minor contributions to the overall fluorescence profile
appear from A and B and can be recognised at 540 nm and
645 nm, respectively. With the aid of relevant model com-
pounds such as TAB2 and TA2C it becomes possible to
estimate the contributions made by individual A - B and
A - C EET steps to the total decay of the A-based excited state
in the cluster. Rate constants of 5.5 1010 s1 (EET efficiency of
99.6%) for the A - B transfer step and of 2.2 109 s1 (EET
efficiency of 90.0%) for the A - C transfer step have been
determined. The difference between these A - B and
A - C EET rates can be used to infer a ‘‘circular’’ route
(i.e., from A to B and finally to C) for the energy-migration
pathway.63
Linear systems
Over the past few decades, considerable research activity Fig. 17 Molecular formulae for phenylethynyl-Bodipy oligomers
has been directed towards the construction of so-called intended as putative photonic wires.
Fig. 18 Molecular formulae for the phenylethynyl-bridged Bodipy
dyes and the modified derivatives bearing a terminal azathio crown
ether.
thereby provides for a virtual Stokes’ shift of 760 cm1 which

exceeds that for a standard Bodipy (being typically around
350 cm1).68 The use of similar synthetic protocols allows
isolation of the homo-Bodipy dyes 42–44 where the terminals
are linked by ethynylphenyl spacers. Quite selective mono-
functionalization is possible on the basis of discrete Knoevenagen
reactions and allows the synthesis of asymmetric derivatives. The

latter compounds are set up to deliver an EET cascade along the
Fig. 19 Molecular formulae for hybrid Bodipy dyes intended as
molecular axis, as exemplified by molecules 45–47 (Fig. 18).70 ratiometric chemosensors.
The relative excited-state energy levels localised on these
latter molecules favour fluorescence from the styryl-modified
derivative while the azathio crown ether is able to accommo- certain compositions of volatile components. An unexpected
date adventitious cations. Now, the concept of an enlarged bonus obtained from compounds such as 49 is the realisation
virtual Stokes’ shift can be seen clearly in as much as the that the unresolved absorption spectrum, arising because of
sensor can be illuminated at a wavelength corresponding to the overlapping transitions, becomes resolved on complexation of
conventional Bodipy dye. Rapid intramolecular EET follows mercury salts. This situation arises from the substantial blue
from such selective excitation and serves to populate the shift of the absorption spectrum of the mono-styryl-Bodipy
lowest-energy, singlet-excited state associated with the styryl- dye carrying the azathiacrown ligand that accompanies cation
substituted Bodipy dye, which is strongly fluorescent in the binding as a result of switching off the internal charge-transfer
absence of a bound cation.70 Clearly, the selection of the effect. Excitation at 540 nm, for example, leads to a five-fold
vinyl-ligand can be readily adapted so as to construct a wide increase of fluorescence at 675 nm when the cation binds to its
range of ratiometric chemosensors intended to function as pocket.71
probes for various pollutants and toxins. For example, a Understanding how the rate of EET evolves as a function of
remarkable perturbation of the EET probability occurs upon molecular length has attracted great attention over recent
binding Hg(II) to the coordination site due to a spectacular years and the subject includes examination of both excited-
absorption spectral shift for the acceptor dye. This shift causes singlet and triplet processes over a wide variety of separation
a significant decrease in the spectral overlap integral, thereby distances. The field is large and outside the scope of the present
curtailing intramolecular EET and disturbing the ratio of the review.72 Even so it is worth drawing attention to the multi-
two fluorescence bands. Indeed, a 35-fold increase of the farious synthetic opportunities provided by contemporary
emission characteristic of the acceptor is realised on saturating Bodipy chemistry as a means by which to engineer sophisticated
the pocket with cation, leading to a marked improvement in D–Sp–A arrays in which three and four disparate chromo-
the detection limits when compared with direct excitation into phores are incorporated into a single molecule.73 We illustrate
the acceptor dye.70b this situation by reference to the preparative pathways
A further advantage of this approach relates to the large sketched in Fig. 20. Reaction proceeds with a step-by-step
choice of coordination pockets that could be appended to the homologation of a yellow Bodipy dye possessing the necessary
chromophore and the versatility of the synthetic procedure functionality for cross-coupling reactions with selected modules
that allows for fine tuning of the system. For example, the able to increase the size of the polyaromatic arm. Such dyes
distance separating donor from acceptor in 45–47 is easily were produced with three, four and five substituted phenylene
varied, the number and location of the binding sites can be units built into the central spacer. Linking these modules to a
changed, and several disparate coordination pockets could be blue expanded Bodipy dye bearing two ethynylphenyl iodo
attached to the same framework.70b Furthermore, an inverted residues at the boron centre gave rise to the target BODN-EXP
EET system is made feasible by constructing molecules where dyes.73 By using a yellow dye decorated at the boron centre
the complexation pocket is linked at the donor portion of the with two ethynylpyrene moieties and with a terminal alkyne at
molecule and using a passive energy acceptor, as in the case of the pseudo-meso-position provided the impetus to isolate the
49 (Fig. 19). Now, by modulation of the excitation energy multi-chromophoric dye Py-BOD0-EXP, where pyrene could
input, ratiometric chemosensors with specific signatures can be be selectively excited with near-UV light (Fig. 21).
designed for selected targets.71 The net result is the ability to A notable feature of this series is that each subunit can be
construct artificial noses capable of the recognition of complex selectively excited with monochromatic light. Highly effica-
mixtures of reagents, with the express purpose of screening for cious EET occurs from the first-excited singlet state localized
Huang–Rhys factor determined by emission spectroscopy.
Both parameters relate to the effective conjugation length.
Direct illumination73 of the spacer unit leads to EET to both
terminals, followed by EET from yellow Bodipy to the blue
version. In each case, EET to the blue dye involves initial
population of the second-singlet excited state whereas transfer
from spacer to the conventional Bodipy dye populates the S2
state for shorter lengths but the S1 state for the longer
analogues. The rate of EET from spacer to conventional
Bodipy dye, as measured for the corresponding molecular
dyads, is extremely fast (>1011 s1) and scales with the

spectral overlap integral. The relative partitioning of EET
from the spacer to each terminal is somewhat sensitive to the
molecular length, with the propensity to populate the conven-
tional Bodipy dye changing from 65% for n = 0 to 45% for
n = 2 (Fig. 20). The most likely explanation for this behaviour
can be traced to the disparate spectral overlap integrals for the

two dyes.
In the molecular tetrad, Py-BOD0-EXP, in which pyrene
residues replace the fluorine atoms present on the yellow
Bodipy-based dye,73 rapid EET occurs from pyrene to the
Bodipy dye and is followed by slower, long-range EET to the
opposite terminal. Such materials are seen as highly attractive
solar concentrators when dispersed in transparent plastic
media and used under conditions where both inter- and
Fig. 20 Molecular formulae for a series of molecular triads based on
intramolecular EET steps operate.
dual yellow/blue Bodipy dyes spaced by oligoethynylphenyl bridges.
on the (conventional) yellow Bodipy dye to its counterpart Spiro-linked dyads

resident on the (expanded) blue Bodipy-based nucleus. The
More than half a century ago, Förster proposed a theoretical
experimental rate constant, kEET, follows a non-linear evolu-
description to explain the mechanism by which EET occurs
tion with separation distance (i.e., the boron–boron separation
between widely-spaced reactants where there is little chance of
distance varies progressively from 18 to 38 Å along the series).
direct orbital contact.74 He was able to relate the rate constant
However, kEET rate falls by only a factor of 4-fold on moving
for through-space EET to the spectral overlap integral, the
from the shortest to the longest spacer. This shallow length
distance between the respective transition dipoles, and the
dependence is a consequence of the energy gap between donor
mutual orientation of the two reagents. This theory has been
and spacer units becoming smaller as the molecular length
accepted and applied, particularly by the biophysics community,
increases. Interestingly, a simple relationship exists between
to an inordinately diverse range of applications. Its main
the measured electronic resistance of the spacer unit and the
strength relates to EET events occurring over separation
distances in excess of 50 Å or so but it is doubtful that it
can be properly applied to closely-spaced reactants. Indeed, in
most of the D–Sp–A systems engineered in the recent past,
EET occurs via two classical routes: a through-bond and
a through-space mechanism. Often both processes run in
parallel and it is difficult to elucidate the dominant effects
for weakly coupled systems.74 This is an especially challenging
problem, exacerbated by growing doubts about the general
acceptability of calculating Förster rates from conventional
theory for molecular dyads.74 In turn, this situation opens up
new opportunities to test Förster theory over short distances
by introducing well-defined molecular assemblies where
through-bond interactions are minimised. In fact, appropriate
dyads have been built around 2,2 0 -disubstituted-9,9 0 -spiro-
bifluorene bridges which are believed to inhibit through-bond
EET by incorporating an orthogonal, non-conjugated connec-
tion into the spacer unit.75
The synthetic strategy used to prepare these new molecular
Fig. 21 Molecular formula of the pyrene-substituted molecular dyads is outlined in Fig. 22 and capitalises on the use of
tetrad. relevant iodophenyl-substituted Bodipy dyes and a racemic
Fig. 23 Schematic representation of the EET processes observed for

the spiro-bridged Bodipy-based dyes 54.
conditions with a rate constant of 2.6 109 s1 (Fig. 23).

The probability of EET, which occurs in competition with

radiative and non-radiative decay of the excited singlet state of
the donor, is approximately 90%. Now, the coupling element
computed from Förster theory (|V| = 0.91 cm1) compares
remarkably well with the experimental value (|V| = 1.21 cm1).75
In further examination of this agreement it was noted that both
the absorption and fluorescence maxima of EXP move steadily
towards lower energy with decreasing temperature due to
changes in the dielectric constant of the solvent. This has the
effect of modifying the spectral overlap integral. The variation in
kEET accurately reflects these changes, thereby confirming that
only coulombic interactions need be considered and further
emphasizing that simple Förster theory works well under these
conditions.
The energy acceptor, EXP, possesses pronounced charge-
transfer effects that are switched off on protonation of the
amine groups and this effect is accompanied by a substantial
blue shift for the respective absorption and fluorescence
maxima. Quite unexpectedly, the rate of EET found for
BOD-EXP(2H+) is only 20% higher than that determined
for the neutral system.75 The experimental coupling element
Fig. 22 Molecular formulae of the spiro-bridged Bodipy-based dyes
(|V| = 0.70 cm1) falls to approximately 60% of that derived
used to critically test Förster theory for EET over short separations.
for the neutral species because protonation leads to disruption
of the transition dipole moment on the acceptor. Under these
mixture of diethynylspirobifluorene.76 Promoting these cross- conditions, the calculated |V| term has a value of 0.97 cm1.
coupling reactions with Pd(0) catalysts facilitates the one-pot Now the agreement between experiment and theory is not so
synthesis of BOD (30%) and BOD-BOD (25%) or EXP (28%) good and the calculation seems to overestimate the coupling
and EXP-EXP (25%) in quite respectable yield. The target by a factor of around two-fold. For the monoprotonated
conjugate BOD-EXP was conveniently prepared in 72% yield species EXP(H+), formed during the early stages of the
from BOD (or EXP) and the iodophenyl-Bodipy counterpart titration, the acceptor possesses increased charge-transfer
using similar protocols. The geometry around the bifluorene character relative to EXP because of the inductive effect of
spacer provides for a perpendicular arrangement77 where the the ammonium ion.75 The spectral overlap integral lies
two boron atoms are separated by about 20 Å. Despite the between those of the neutral and dicationic forms. In this
unsaturated and orthogonal bridging unit, EET is highly case, agreement between experiment (|V| = 0.46 cm1) and
efficient and reflects the fact that the main mechanism involves theory (|V| = 0.20 cm1) worsens due to the poor definition
through-space interactions. Thus, excitation of BOD-EXP in of the transition dipole moment vector on the acceptor.
CH3CN at 480 nm results in selective population of the first- Incidentally, this system functions as an excellent fluores-
excited singlet state resident on the BOD unit. Weak fluorescence-based thermometer in organic solvents.
cence can be detected at 540 nm and assigned to BOD by The same molecular dyad has been subjected to a detailed
reference to model compounds; in addition there is strong examination of how changes in solvent polarity influence the
fluorescence from the EXP moiety. For the BOD component, rate of intramolecular EET.78 This study is made possible by
both FF and tS decrease relative to the reference molecules, the realisation that whereas the BOD terminal is insensitive to
and it is clear that intramolecular EET occurs under these changes in solvent the charge-transfer character inherent to
EXP renders that terminal particularly sensitive to the
nature of the surrounding environment. In all solvents, the
probability of EET exceeds 90% but the rate shows a clear
increase in non-polar solvents. This effect is traced to small
perturbations of the optical absorption spectrum of the
acceptor, which affects the overlap integral for Förster-type
EET and also disturbs the accompanying transition dipole
moment. There is an additional subtle effect whereby the
nature of the surrounding solvent affects the transition dipole
density, which itself modifies the separation distance.78
Water-soluble cassettes
We have emphasized throughout this review the need to design
highly fluorescent dyes that possess a relatively large Stokes’ Fig. 24 Water-soluble cassettes for fluorescence imaging of living
shift. The main application of such materials lies in the field of cells as adapted from ref. 82.
fluorescence microscopy, including flow cytometry, where the

dye is used to image parts of intact biological cells or tissue. involved anchoring dyad 55 to bovine serum albumin
Most luminescence microscopes utilise a system of optical (BSA, X2 in Fig. 24) to give a stable conjugate that survived
filters to isolate excitation and emission beams and, since these several acid–base cycles.82 The BSA-55 conjugate could be
filters must be non-emissive, the range of cut-off wavelengths is imported into specific cells via a carrier and the resultant
rather restricted. This makes it extremely difficult to use dyes ratiometric signatures used to determine the local pH inside
with a small Stokes’ shift, regardless of their fluorescence the cell.
quantum yield. The use of Bodipy dyes with an enhanced Along similar lines, the construction of two additional
(i.e., virtual!) Stokes’ shift overcomes this experimental limita- cassettes using the same energy donor but different acceptors
tion and the new molecular dyads based on intramolecular (lem at 599 and 645 nm) were synthesized using ‘‘click chemistry’’
EET have important outlets in this area. Even so, there is far (Fig. 25). The innovation here lies with the use of a water-
more to the development of useful imaging dyes than their soluble sulfonic acid derivative as the energy donor in
having an amplified Stokes’ shift.79 In particular, new labels conjunction with a constrained Bodipy-based acceptor, the
have to be designed in such a way that the fluorescence synthons being connected by a 1,2,3-triazole linker. The
maxima fall within the far-red window (i.e., 650–800 nm) in fluorescence quantum yields reach 30 and 24%, respectively,
order to avoid auto-fluorescence from the biological host and for 56 and 57 in water at pH = 7.4 while both compounds
to avoid back-scattering contamination. Since most commer- exhibit highly efficient EET processes. The pseudo-Stokes’
cial fluorimeters have limited sensitivity at long wavelengths, shifts are 3300 and 4500 cm1, respectively, for 56 and 57.
the ideal emission wavelength is around 700–750 nm. These Interestingly, labelling spretavidin with cassette 56 and avidin
dyes must also be resistant to self-aggregation in aqueous with cassette 57 leads to an unusual three-component set-up
media or in the cell membrane, hence attention must be given when both conjugate Strep-56 and Avi-57 associate with a
to their inherent solubility. This leads to a demand to develop single BSA-Atto-425 (lem at 425 nm) labelled protein.83
water-soluble dyes that readily undergo bio-conjugation or cell On mechanistic grounds it is useful to note that there is little
internalisation. Although various water-soluble fluorescein– spectral overlap between Atto-425 emission at 480 nm and
rhodamine dyads80 have been reported as reagents for intra- absorption of the fluorescent residues at 600 and 645 nm.
cellular imaging in the past,22,33 we recognise the need to
produce suitable Bodipy-based analogues that are adequately
soluble in water.81
Recently, water-soluble Bodipy-fluorescein cassettes have
been described as ratiometric pH reporters by which to image
protein-dye conjugates in living cells (Fig. 24).82 These novel
materials were prepared using Sonogashira coupling of
5 0 -alkynylfluorescein diacetate with an appropriate diiodo-
Bodipy derivative, followed by removal of the acetate group.
Here, the efficiency of EET from the xanthene (i.e., fluorescein)
donor to the Bodipy acceptor is governed by the pH; hence the
realisation that the dyad can be used as a sensitive pH probe
by which to monitor intracellular physiological conditions. It
was reported that EET from fluorescein to Bodipy is effica-
cious in acidic solution giving rise to emission at 600 nm for an
input at 495 nm. Conversely, EET was completely suppressed
in basic media where the phenolate form of the xanthene dye Fig. 25 Water-soluble cassettes for bio-labelling and multi-FRET in
fluoresces at 520 nm. Further development of this system the essays described further in ref. 83.
However, spectral overlap is very strong between Atto-425
emission and absorption by the tetramethyl-Bodipy fragment.
This finding suggests that the latter dye functions as a relay
by which to promote a cascade EET process (Fig. 26).
Further developments using related conjugates have led to
the discovery of dedicated residues able to monitor specific
protein–protein interactions both in vitro and inside living cells
as probed by fluorescence microscopy.83
Hybrid derivatives based on Bodipy dyes

Subphthalocyanine analogues
In recent years there has been a rapid upsurge in non-biological
applications of EET, including solar energy conversion,84–86
information processing in molecular devices and machines,87

and the detection of analytes using molecular-based sensors.88
As progress in these areas develops, there comes the need to
identify new reagents with predetermined optical properties
and discrete chemical signatures. The field is continually
evolving and new materials appear at regular intervals. For Fig. 27 Examples of hybrid subphthalocyanine–Bodipy covalently-
example, with respect to the design of advanced substrates for linked dyads as adapted from refs. 90 and 91.
broad applications in electroluminescence, non-linear optics
and laser technology, it appears that the subphthalocyanine The absorption spectrum of 62 is a linear combination of
(SubPc) motif holds particular attractions. This constricted the individual spectra without noticeable perturbations, a
form of phthalocyanine possesses a 14p-electron, bowl-shaped result in keeping with the absence of orbital overlap between
conformation having C3v symmetry. Problems from poor the SubPc core and the axially linked dye. The absorption
solubility, and the usual difficulty caused by a small Stokes’ band at 707 nm (e = 101 000 M1 cm1) belongs to the S0–S1
shift, can be overcome by attaching a Bodipy fragment to the transition of the Bodipy fragment and that at 568 nm
SubPc core via a covalent linkage at the boron centre, as was (e = 94 000 M1 cm1) to the Q band of the SubPc unit.
done earlier for Bodipy derivatives. Indeed, the Grignard Interestingly, excitation at 670, 555 or 430 nm results in
chemistry developed for Bodipy that allows us to replace the fluorescence centred at 762 nm with a quantum yield of 0.18,
fluorine atoms with alkyne functions was further adapted to which is clearly due to the Bodipy fragment. The fluorescence
modify the SubPc unit and represents a neat entry to novel spectrum shows excellent mirror symmetry with the lowest-
D–Sp–A dyads (Fig. 27).89 The direction of intramolecular energy absorption transition while the emission lifetime is
EET between the Bodipy and SubPc fragments can be tuned 4.1 ns. Almost no residual emission from the SubPc, expected
by changing the nature of the Bodipy or by changing the pH. at 574 nm, can be seen. Such behaviour is indicative of efficient
Typical examples are given in Fig. 28. Thus, while 63 under- energy transfer from the SubPc to the Bodipy moiety. In this
goes singlet-to-singlet EET from the tetramethyl-Bodipy to the way, the Stokes’ shift expands from 250 to 4900 cm1.
SubPc90 the direction is reversed for 64. Electron transfer from the dimethylamino fragment to
the SubPc singlet-excited state was not observed, despite a
Fig. 26 Symbolized EET from a BSA-Atto425 (BLUE) labelled

protein to two different cassette dyes labelled with streptavidin
Strep-51 (PINK) and avidine Avi-52 (GREEN) as adapted from Fig. 28 Representation of the energy-transfer pathways found for
ref. 83. selected hybrid SubPc–Bodipy dyads.
favourable thermodynamic driving force (DG = 0.28 eV).
This is consistent with the axial linkage inhibiting through-
bond electronic interactions, whilst facilitating through-space
energy transfer, and with the large spatial separation between
the reactants (Fig. 28).91
Stepwise addition of HCl to compound 62 brings
about a pronounced blue-shift for the fluorescence maximum
(lem = 634 nm; FF = 0.26, tS = 4.7 ns).91 After protonation
of both dimethylamino groups, illumination into the SubPc
fragment at 532 nm results in virtually complete EET to the
emissive state of the dicationic Bodipy species. This behaviour

can be well explained in terms of the improved spectral overlap
integral for Förster-type energy transfer, arising from the
significant hypsochromic shift and increased oscillator
strength that accompanies protonation.
Organometallic fragments
One of the main reasons why Bodipy-based dyes are photo-
chemically stable is because intersystem crossing to the triplet
manifold is ineffective, even when heavy atoms are substituted
into the molecular framework or surrounding environment.
With conventional Bodipy dyes, triplet formation accounts for
less than 5% of the photon balance. The triplet-excited state
Fig. 29 Examples of hybrid Bodipy dyes decorated with cationic
can be observed by laser flash photolysis,92 having a lifetime in
transition-metal complexes.
the absence of oxygen of around 200 ms in fluid solution, and
there is a solitary report of phosphorescence from a Bodipy intercomponent charge-separated state. At 77 K, charge
dye in a glassy matrix at 77 K.93 The latter study indicates a separation is inhibited on thermodynamic grounds and the
large energy gap between singlet and triplet excited states and expected Bodipy fluorescence is restored. In addition, long-
this situation contributes towards the relative slowness of lived (t = 50 ms at 77 K) phosphorescence from the Bodipy
intersystem crossing. In order to examine properties associated triplet-excited state is seen at 775 nm.92 The mechanism
with the Bodipy triplet manifold it becomes necessary leading to formation of the Bodipy triplet state most likely
to sensitize triplet population and this can be done most involves a combination of enhanced spin–orbit coupling and
conveniently by attaching a transition-metal complex to the direct participation of the low-lying, metal-to-ligand charge-
dye in such a way as to favour intramolecular electron and/or transfer (MLCT) triplet-excited state of the metal complex,
energy transfer processes.94 This approach, which is fruitful in which lies at higher energy than the Bodipy triplet.
terms of fundamental knowledge, also leads to important In the case of 66a, fluorescence from the terminal Bodipy
applications in the fields of artificial photosynthesis, energy- dye is extensively quenched due to intramolecular electron
conversion devices (e.g., organic light emitting devices and transfer.96 Although the triplet-excited state of the Bodipy dye
solar cells), and optical microscopy (e.g., cell imaging or two lies at lower energy than the charge-separated state, charge
photon absorption). The same strategy has been used in recombination occurs preferentially to reform the ground
reverse to stabilise the triplet lifetime of the appended metal state. Triplet state formation is relatively unimportant as
complex by setting up an equilibrium with the excited-triplet regards deactivation of the charge-separated state, but there
state resident on the organic moiety, usually pyrene. Indeed, is still an impressive increase in the rate constant for inter-
this latter rationale has been highly successful in prolonging system crossing (kISC) relative to the parent Bodipy dye. This
the triplet lifetime of certain ruthenium(II) and osmium(II) rate is less than ca. 5 105 s1 for 66b, whereas for the Zn
poly(pyridine) complexes.95 Taking advantage of the synthetic complex 66a, kISC increases to around 5 108 s1. The
know-how gleaned during these earlier trials, several Bodipy orthogonal geometries inherent to 66a should give rise to a
dyes have been attached to phosphorescent transition metal large spin–orbit coupling matrix element and additional spin
complexes. In addition to transforming the photophysical orbital coupling is favoured via the heavy-atom effect. The fact
properties by providing indirect access to the triplet state, that triplet formation does not dominate over charge recombi-
the metal complex introduces marked changes in solubility nation is considered to be a consequence of the poor spin–
since many such residues carry an electronic charge. The orbital coupling properties of the parent dye. The rate of
synthesis of these dyads is now straightforward and could be singlet–singlet energy transfer from the Zn complex to the
realized routinely on large scales (Fig. 29). Bodipy dye exceeds 5 1010 s1. The most likely mechanism
For dyad 65, where Bodipy is attached to a ruthenium(II) involves Förster-type, dipole–dipole interactions since there is
bis(2,2 0 :6 0 ,2 0 0 -terpyridine) complex, phosphorescence from strong spectral overlap between fluorescence from Zn-terpy
the Ru-based subunit and fluorescence from Bodipy are and absorption by Bodipy and almost optimal orientation of
quenched at room temperature due to the formation of an the relevant transition dipoles.
Fig. 31 Synthetic route to the C60/Bodipy molecular dyad.
held in an orthogonal geometry.101 Such geometries are

(almost) inevitable if the connection is made via the meso
position of the Bodipy dye. From a synthetic viewpoint
attachment of Bodipy to a C60 residue is made feasible by
first preparing two functionalized precursors that can be
Fig. 30 Top: Energy levels (not to scale) and deactivation pathways joined by classical Pd(0) promoted cross-coupling reac-
for complex 67. Bottom: Transient absorption difference spectra of tions as outlined in Fig. 31.102 The solubility of the target
complex 68 in deaerated CH2Cl2 measured for excitation at 355 nm dyad 69 is ensured by replacement of the fluorine atoms with
(black) or 510 nm (red). Inset: Single wavelength decay trace at 500 nm
hydrocarbon chains.
(black) along with the corresponding single-exponential fit (red) and
An interesting, although far from unique, feature of dyad 69
residuals (green).
is that according to spectroscopic and cyclic voltammetry
measurements both light-induced electron transfer (PET)
Replacing Zn(II) with Pt(II) promotes EET from the
and EET are possible. In non-polar solvent, PET is thermo-
Pt-based MLCT triplet-excited state to the Bodipy triplet
dynamically uphill and the singlet–singlet EET from Bodipy to
(lem at 777 nm; t = 74 ms at 77 K) at both room temperature
C60 is followed by fast intersystem crossing to populate the T1
and 77 K.97 The rate constant for triplet–triplet energy transfer
state localized on the C60 unit. Since the triplet states localised
is about 7 108 s1. In this case, Bodipy fluorescence is not
on the Bodipy and C60 are close in energy, a thermal equili-
quenched although an oxidative photo-induced electron transfer
brium is established and decays with a lifetime of about 140 ms
is thermodynamically feasible (Fig. 30). In the Ir complex, 68,
under anaerobic conditions (Fig. 32). In polar solvent, there is
excitation of either the organometallic fragment or the Bodipy
a large driving force for PET and the charge transfer state
dye leads to population of the Bodipy triplet-excited state.
(CTS) energy is set by the solvent polarity.102 The key feature
This finding was reached on the basis of transient absorption
of this system is the realization that the CTS undergoes partial
spectroscopy and luminescence measurements at 77 K. In
charge recombination to form the triplet state localized on the
this case, phosphorescence from the Bodipy triplet occurs at
C60 residue. Despite the comparable triplet energies for Bodipy
730 nm with a lifetime of 25 ms.98
and C60 there is no experimental evidence for charge recombi-
Molecular dyads containing fullerene units nation forming the Bodipy triplet (Fig. 32). It is notable
that direct intersystem crossing is considerably faster in C60
A tremendously popular research field, which has been in
(kISC E 7 108 s1) than in Bodipy (kISC E 2 106 s1).
vogue for almost four decades, concerns the design of molecular
Furthermore, charge recombination to form the C60 triplet
systems intended to mimic some of the essential features of the
natural photosynthetic apparatus.2,4a,17,18 Many of the more
recent models to emerge from this work have included full-
erenes, most notably C60, as the primary electron acceptor.99
This work has led to the discovery of unusually long-lived,
charge-separated lifetimes (i.e., up to 23 ms) in supramolecular
triads incorporating a C60 electron reservoir.100 The challenge
to us was to devise Bodipy/C60 molecular dyads able to
undergo charge separation under illumination and to examine Fig. 32 Outline of the various processes observed following pulsed
the possibility to generate the Bodipy excited-triplet state excitation of either subunit for 69 in toluene (left-hand side) or in
during subsequent charge recombination. Triplet formation MTHF (right-hand side). Keys: EnT = electronic energy transfer,
is often promoted by charge recombination in sterically- ISC = intersystem crossing, NR = nonradiative decay, ElT =
constrained systems in which the redox-active subunits are electron transfer.
involves hole transfer from the HOMO whereas formation of dimer is about 4800 cm1 whereas that for the monomer is
the Bodipy triplet demands electron transfer to the LUMO. only 420 cm1.
The results are consistent with hole transfer having the larger Co-facial Bodipy dimers have been synthesized recently
electronic coupling element. Similar reasoning can be used to under conditions where the dihedral angle between the two
explain why T1–T1 energy transfer is so slow in 69. planes can be varied, as sketched in Fig. 34.106 Standard
synthetic procedures were used whereby pyrrole condensation
Covalently-linked dimers formed from Bodipy residues with an carbaldehyde in acidic conditions provided the inter-
In common with most other organic dyes, Bodipy chromo- mediate dipyrromethane compounds, which were readily
phores self-associate under certain conditions. Often, aggrega- oxidized to the conjugated dipyrromethene cyanine in the
tion is driven by the solvatophobic effect and depends presence of a Lewis acid under basic conditions. Interestingly,
markedly on the structure of the dye. The dimer tends to the X-ray molecular structure of dye 74 shows pronounced
absorb at relatively long wavelength, typically around 600–650 nm, F F interactions which prohibit perfect face-to-face overlap,
but does not fluoresce. Different types of dimer, according to a feature that prevents optimum p-stacking between the
the alignment of the transition dipole moments, can co-exist neighbouring Bodipy subunits. As a consequence, the level
with the composition of the mixture being highly sensitive to of exciton coupling is less pronounced for 74 compared to 70.
These dimers were sufficiently soluble to allow recording cyclic
the solvent and/or temperature. These aggregates serve no

useful purpose. More valuable information becomes available voltammograms under both oxidative and reductive condi-
from studying flexible chains bearing Bodipy-based terminals tions. It was observed that modest splitting of the reduction
since self-association of the dyes, which leads to perturba- waves was matched by pronounced splitting of the oxidation
tion of the photophysical properties, can report on the local peaks due to delocalization of the electronic charge over the
environment.103 In extreme cases, where strong overlap two Bodipy moieties. Further information on the effects of
exists between the mutual p-systems, exciton coupling can be charge delocalization was sought from spectro-electrochemical
observed.104 Uncertainties in the molecular topology are over- experiments which revealed formation of an intervalence
come by using well-defined dimeric Bodipy derivatives of the charge-transfer (IVCT) band centred at around 800 nm on
type depicted in Fig. 33. Thus, dimers can be prepared from oxidative scans. This IVCT band is attributed to electron
the relevant 2,2 0 -bis-dipyrrins in the presence of excess boron exchange between co-facially arranged neutral and mono-
trifluoride etherate.105 The isolated material, 70, exhibits oxidized Bodipy units.105 One of the dimers has been reported
exciton splitting of ca. 2600 cm1 in the absorption spectrum, to display excimer-like fluorescence in solution.107
with well-defined maxima at 489 nm (e = 72 000 M1 cm1)
and 558 nm (e = 82 600 M1 cm1). Surprisingly, the dimer is
highly fluorescent (FF = 0.67, tS = 3.4 ns) with a maximum Concluding remarks
centred at 638 nm. The corresponding monomeric dye In this review we have focused on recent developments in the
71 exhibits a single absorption band centred at 526 nm synthesis of Bodipy derivatives that retain applications in the
(e = 72 600 M1 cm1) with an emission peak located at generic field of EET. The synthetic versatility of Bodipy dyes
538 nm (FF = 0.88; tS = 5.0 ns). The Stokes’ shift for the has been exposed by new methodologies for selective func-
tionalisation at the dipyrrin and boron sites, augmented by the
easier attachment of residues at the meso position. The new
approaches can be used to produce asymmetric compounds
comprising a wide variety of peripheral units that enrich the
Fig. 33 Synthetic route used for the preparation of meso-aryl substi- Fig. 34 Preparative route used for the co-facial Bodipy dimers
tuted dimeric Bodipy dyes as adapted from ref. 104. adapted from ref. 105.
absorption spectral profile. Selective illumination into these Notes and references
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Volume 47 | Number 2 | 2011

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www.rsc.org/members FEATURE ARTICLE

Artiﬁcial light-harvesting antennae: electronic energy transfer by way of

Doctor Raymond Ziessel Professor Anthony Harriman

absorbers to soft matter (e.g., liquid crystals, organo-gelators,

shift). A small Stokes’ shift leads to severe problems with

Fig. 4 Examples of anthracene-linked Bodipy dyes as adapted from

Fig. 10 Examples of a molecular triad and tetrad comprising,

is notable that the various appendages have minimal eﬀect on

that determined (kRAD = 4.4 107 s1) from the Strickler–

Fig. 12 Schematic representation of sequential EET processes as

subunit. The rates of intramolecular EET were determined

Fig. 14 Presentation of the rate constants for intramolecular EET

the upper-lying excited state. Not much is known about the S2

fragments identiﬁed as a building block for such wires is the

tion of a variety of mixed compounds (TAB2, TA2C, TB2C, TBC2,

thereby provides for a virtual Stokes’ shift of 760 cm1 which

reactions and allows the synthesis of asymmetric derivatives. The

dyads, is extremely fast (>1011 s1) and scales with the

can be traced to the disparate spectral overlap integrals for the

on the (conventional) yellow Bodipy dye to its counterpart Spiro-linked dyads

Fig. 23 Schematic representation of the EET processes observed for

conditions with a rate constant of 2.6 109 s1 (Fig. 23).

The probability of EET, which occurs in competition with

ﬂuorescence microscopy, including ﬂow cytometry, where the

Hybrid derivatives based on Bodipy dyes

information processing in molecular devices and machines,87

Fig. 26 Symbolized EET from a BSA-Atto425 (BLUE) labelled

emissive state of the dicationic Bodipy species. This behaviour

Fig. 31 Synthetic route to the C60/Bodipy molecular dyad.

held in an orthogonal geometry.101 Such geometries are

the solvent and/or temperature. These aggregates serve no

6 M. Y. Okamura, G. Feher and N. Nelson, in Photosynthesis.

A. Harriman and J. P. Rostron, Chem.–Eur. J., 2005, 11, 7366. 2183.

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