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Structural modification strategies for the rational

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design of red/NIR region BODIPYs†

Cite this: Chem. Soc. Rev., 2014,
43, 4778
Hua Lu,ab John Mack,c Yongchao Yanga and Zhen Shen*a
This review focuses on classifying different types of long wavelength absorbing BODIPY dyes based on
the wide range of structural modification methods that have been adopted, and on tabulating their
spectral and photophysical properties. The structure–property relationships are analyzed in depth with
Received 17th January 2014 reference to molecular modeling calculations, so that the effectiveness of the different structural modifi-
DOI: 10.1039/c4cs00030g cation strategies for shifting the main BODIPY spectral bands to longer wavelengths can be readily com-
pared, along with their effects on the fluorescence quantum yield (FF) values. This should facilitate the
www.rsc.org/csr future rational design of red/NIR region BODIPY dyes for a wide range of different applications.
1. Introduction and optical sensors for biological and medical applications.1–6

For the latter, it is advantageous to work in the red/NIR region
Over the past decade there has been considerable interest in of the spectrum because of the so-called biological window in
the synthesis of organic chromophores with strong absorption the 650–1000 nm region, where autofluorescence, and absorption by
and fluorescence bands in the near-IR (NIR) region primarily water, tissues and cells are minimized, and there is less light
because of advances in optical techniques for imaging, in scattering. This means that deeper penetration by incident laser
microarrays, and in electrophoresis, and the need for labels light (2–5 cm) can be achieved in what is sometimes also described
as the therapeutic window.7–11 These factors, together with the
a
State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of development of low-cost NIR region excitation sources and detectors,
Microstructures, Nanjing University, Nanjing, 210093, P. R. China. have inspired the design of new fluorophores or fluorescent
E-mail: [email protected] materials,12–22 with high molar absorption coefficients and
b
Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of fluorescence quantum yield (FF) values in this spectral region.23
Education, Hangzhou Normal University, Hangzhou, 311121, P. R. China
c Until recently, cyanine dyes, such as Cy3 or Cy5, have been
Department of Chemistry, Rhodes University, Grahamstown, 6140, South Africa
† This review is dedicated to Professor Xiaozeng You on the occasion of his 80th the fluorochrome of choice in many biological applications, but
birthday. issues related to their poor photostability and low FF values are
Dr Hua Lu received his PhD Dr John Mack obtained a BSc

degree from Nanjing University (Hons) degree with first class
(2010) under the supervision of honours from Aberdeen University
Professor Zhen Shen. He is an (1988) and received a PhD at the
associate professor at the Key University of Western Ontario
Laboratory of Organosilicon (1994) for research on phthalo-
Chemistry and Material cyanine anion radicals under the
Technology of the Chinese supervision of Professor Martin
Ministry of Education at J. Stillman. He subsequently
Hangzhou Normal University. carried out spectroscopic research
His research focuses on dyes and on porphyrins, phthalocyanines
pigments with the photophysics, and BODIPYs at the University of
Hua Lu DFT calculations and biological John Mack Western Ontario and Tohoku
imaging of BODIPYs being of University. He works as a senior
particularly strong interest. researcher in the Department of Chemistry at Rhodes University in
South Africa. There continues to be a strong focus on porphyrinoids and
BODIPYs within his research.
4778 | Chem. Soc. Rev., 2014, 43, 4778--4823 This journal is © The Royal Society of Chemistry 2014
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Review Article Chem Soc Rev
often encountered. Rotation and photoisomerization of their

flexible structures often result in nonradiative deactivation
pathways.24–26 Even for more rigid or bridged cyanines, the
remaining flexible bonds can still provide effective funnels for
nonemissive deactivation.27,28 Rhodamine dyes are often used as
Fig. 1 The ‘‘BODIPY’’ fluorophore and its IUPAC numbering system. The 8-
alternatives, owing to their structural rigidity. Rhodamine and position is often referred to as the meso-carbon, while the 3,5-positions, and the
fluorescein dyes exhibit high FF values, even in aqueous solvents. 2,6- and 1,7-positions are referred to as the a- and b-carbons. Delocalized
Their use in biological applications is problematic, however, resonance structures of BODIPY are provided with the formal charges indicated.
since their absorption and emission maxima lie well below
600 nm.3,29,30 Moreover, since they are positively charged ions,

the solubility of rhodamines is generally restricted to highly polar BODIPY chromophore are typically limited to the 470–530 nm
solvents and the effect of the counter ion for the dye also has to region.50–55 Marked red-shifts of the absorption and emission
be taken into consideration in any application.31 maxima have been achieved through aryl, ethynylaryl and styryl
Boron-dipyrromethene (4,4-difluoro-4-bora-3a,4a-diaza-s- substitution at the 1-, 3-, 5-, and/or 7-positions, aromatic ring
indacene, BDP or BODIPY) fluorescent dyes, a structural analo- fusion, by replacing the meso-carbon atom with an aza-nitrogen
gue of the porphyrins, have been the focus of considerable atom to form an aza-BODIPY, or combinations thereof (Fig. 1).50
research interest over the last three decades.32–41 The synthesis Earlier reviews on BODIPY chemistry have covered the
of BODIPY dyes was first described by Treibs and Kreuzer in synthesis and spectroscopic properties of BODIPY dyes, as well as
1968.42 Since the mid-1980s, their use as solid-state solar their applications in fluorescent indicators, photodynamic therapy,
concentrators has also been explored.43–49 BODIPYs subse- luminescent devices and energy transfer cassettes.32–37,39,40 There has
quently started to be used extensively as laser dyes, fluorescent also been a strong focus on the versatility of the BODIPY core with
stains and labels in fluorescence imaging, and as indicator dyes respect to functionalization.35 This review is dedicated to classifying
in sensor applications. In recent years, the number of papers different types of long wavelength BODIPY based on the wide range
being published on the synthesis and properties of BODIPY of structural modification strategies that have been adopted and on
dyes has been growing rapidly.34,37–41 This has been related to tabulating their spectral properties. The structure–property relation-
(i) their facile synthesis and structural versatility, (ii) their ships are analyzed in depth with reference to molecular modeling
excellent spectroscopic properties (narrow Gaussian-shaped calculations, so that the effectiveness of the different strategies can be
absorption and emission bands, high molar extinction coefficients readily compared, along with their impact on the FF values. This
(usually e 4 80 000 M1 cm1) and FF values (commonly F 4 should greatly facilitate the future rational design of red/NIR BODIPY
0.50), moderate redox potentials, negligible triplet-state formation dyes with properties suitable for applications.
and negligible sensitivity to solvent polarity, excellent photo- In recent years, there has also been considerable interest in
stability, and high solubility in commonly used organic solvents the incorporation of BODIPY fluorophores into energy-transfer
of differing polarities), and (iii) their wide range of potential cassettes and polymers.22,34,56,57 This research is not included
applications in numerous research fields.32,33,37–40 A major draw- since this review focusses on the modification of the BODIPY to
back, however, is that the spectral properties of the classic long wavelengths. The exchange of the two fluorine atoms at
Dr Yongchao Yang received his Prof. Zhen Shen received a PhD

PhD degree on the design and degree from Nanjing University
synthesis of novel near-infrared (2000) under the supervision of
BODIPYs for bioimaging and Professor Xiao-Zeng You. After
photodynamic therapy from postdoctoral research for one year
Nanjing University (2013) under with Prof. Jörg Daub at
the supervision of Professor Regensburg University, Germany,
Zhen Shen. and for two years with Prof.
Noboru Ono at Ehime University,
Japan, on a fellowship from JSPS,
she joined the State Key
Laboratory of Coordination
Yongchao Yang Zhen Shen Chemistry, Nanjing University, in
2003. She became a full professor
in 2007 and received a SPP/JPP Young Investigator Award for her
research in porphyrin chemistry in 2010. Her research interests are
mainly focused on the synthesis, spectroscopic properties and
biological applications of BODIPYs and porphyrins.
This journal is © The Royal Society of Chemistry 2014 Chem. Soc. Rev., 2014, 43, 4778--4823 | 4779
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Fig. 2 MO energies of a C12H122 cyclic perimeter, BODIPY and a C12H10N2 model compound.
the boron centre with another anion provides another route for lifting of the degeneracies of the MO energies due to the C2v
functionalizing these dyes.58–70 Since this typically results in symmetry. This results in a HOMO and LUMO that are well-
almost no change in the wavelength maxima, however, these separated in energy terms from the other p-system MOs.
structures are not included here. Readers interested in these Theoretical calculations predict that the lowest-lying S0 - S1
topics should consult the relevant literature. transition is almost entirely associated with the HOMO -
LUMO transition.71 The a2 MOs with a short-axis nodal plane
passing through the boron atom are largely unaffected in
2. Electronic structures and optical energy terms relative to a C12H10N2 heteroaromatic model
properties of BODIPY chromophores compound, while the b2 MOs with nodal planes aligned with
the long-axis are significantly stabilized due to stronger bond-
2.1 BODIPY p-conjugation system ing interactions between the two pyrrole moieties, larger MO
Although BODIPY dyes do not formally fit Hückel’s rule for coefficients on the electronegative nitrogen atoms, and the
aromaticity, their properties are broadly similar to those of crosslinking between atoms on the outer perimeter due to the
aromatic p-systems, since the coordination of the boron atom incorporation of the two pyrrole moieties.71
holds the dipyrromethene ligand in a rigidly planar conforma- From the standpoint of obtaining a red-shift of the main
tion. The p-MOs associated with the indacene plane can be absorption and emission spectral band, a structural modifica-
compared to those of an aromatic C12H122 cyclic perimeter, tion must alter the energies of the two frontier p-MOs in a
which has MOs arranged in a ML = 0, 1, 2, 3, 4, 5, 6 manner that narrows the HOMO–LUMO gap. Aryl-substituents
sequence in ascending energy terms (Fig. 2). The angular nodal can be added at the meso-carbon. Although the inductive effect
patterns for the p-MOs of an unsubstituted BODIPY dye follow a of these substituents will usually have a similar effect on the
similar sequence, but the introduction of the BF2 moiety, the energies of the HOMO and LUMO, the mesomeric effects can
cross links and pyrrole nitrogen atoms results in a marked differ significantly.72–74 The interaction between the p-systems
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Fig. 4 Absorption and emission spectra of 1,3,5,7-tetramethyl-meso-

phenyl-BODIPY, lex = 470 nm.
Fig. 3 Nodal patterns of the HOMO and LUMO of an unsubstituted

BODIPY model compound at an isosurface of 0.07 a.u. values, since there is a very low rate of nonradiative decay. Any
structural modification, which results in a greater degree of
conformational flexibility, will tend to result in a lower fluores-
typically has only a minor effect on the energy of the HOMO,
cence quantum yield. Another reason for the high FF values is
since there is a nodal plane at the meso-carbon, but changes
that there are relatively low rates of intersystem crossing (ISC).
to the para-substituent on a phenyl substituent can have a
This is an advantage for applications that depend on the
significant impact on the energy of the LUMO, since there is a
intensity of the fluorescence emission band, but there are other
large MO coefficient at this position. The effects of substituents
potential applications such as photodynamic therapy which
at the 1,7-, 2,6- and 3,5-positions of the BODIPY structure
could make use of the red/NIR region dye properties of struc-
(Fig. 3) can be rationalized in a similar manner. There is a
turally modified BODIPYs, where this is not advantageous. In
nodal plane near the 2,6-positions in the LUMO but not in the
the last few years, heavy-atom-functionalized BODIPY dyes have
HOMO, while there are nodal planes near the 1,7-positions in the
been reported which exhibit enhanced rates of ISC and hence
HOMO but not in the LUMO. Although there are no nodal planes,
higher singlet oxygen quantum yields.37,39
there are larger MO coefficients at the 3,5-positions in the HOMO
than in the LUMO. In each case, there is scope for narrowing the 2.3 The formation of nonradiative S1 states
HOMO–LUMO gap based on the mesomeric effects of substituents
when there is an extension of the p-conjugation system.71 The fluorescence intensity of structurally modified BODIPY
dyes can be quenched in polar solvents due to an enhancement
of the rate of nonradiative decay via what are often referred to
2.2 Optical properties of BODIPY as intramolecular charge transfer (ICT) states.84–87 ICT states
Generally, the absorption spectra of BODIPY dyes contain are derived from the S1 state of the fluorophore and are caused
narrow spectral bands with two absorption maxima in the by a separation of charge on different portions of the structure
visible region: (i) the intense 0–0 band of the S0–S1 transition upon electronic excitation. The rate of nonradiative decay is
and (ii) a more or less pronounced shoulder on the high-energy believed to be enhanced by the formation of conical intersections
side of the main band, which is attributed to the 0–1 vibrational between this low-lying non-emissive S1 state and the ground
transition (Fig. 4). Additionally, weaker broad absorption bands state.84–87 It has been demonstrated that the charge-separated
at shorter wavelengths can be assigned to S0–Sn (n Z 2) character of the non-emissive S1 state is enhanced when there is a
transitions.75–82 When the BF2 moiety is removed from the twisting of the bond linking the donor and acceptor moieties.85,86
BODIPY structure, the structure is converted into the all-trans Another important quenching mechanism for the S1 state is
conformation and the chromophore is converted into a type of referred to as photoinduced electron transfer (PET).73,88–96
cyanine dye. Cyanine dyes undergo trans–cis isomerization In this context, an electron receptor and the fluorophore
upon electronic excitation, which quenches the fluorescence.83 are usually separated by a short alkyl spacer, electronically
The favorable properties of BODIPY dyes for fluorescent dye disconnecting the p-electron systems of the receptor and fluoro-
applications can largely be attributed to their rigid planar phore. The PET process is followed by nonradiative decay to the
structures. The potential energy surfaces of the S0 and S1 states ground state. The Marcus theory97 gives a quantitative description
are very similar, so narrow Gaussian-shaped absorption and of the kinetics of electron transfer if the coupling between the
emission bands are typically observed for the lowest energy initial and final states is well accounted. The PET process can be
transition. The rigidity of the p-system also leads to high FF described pictorially in terms of molecular orbital (MO) theory,98
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and this has become a powerful tool for analyzing the fluorescence reactions and Sonogashira alkynations.113–121 The reaction
‘‘on–off’’ problem.99,100 In the unbound state, after excitation, the conditions can be adjusted so that either mono- or disubstituted
fast electron transfer from the receptor to the fluorophore products are formed. These nucleophilic substitution and cross-
quenches the fluorescence of the system. When the receptor is coupling reactions of 3,5-dichloroBODIPY represent a very successful
bound, the receptor redox potential is perturbed and slows down approach for preparing a wide variety of BODIPY compounds, which
the PET process, reviving fluorescence emission. This logic absorb and emit in the red/NIR region. These types of reactions
indication process can also be reversed.92 From the standpoint can also be utilized with BODIPYs that have been halogenated at
of Kasha’s rule,101 the ‘‘on-off’’ process of the fluorescence the 2,6- and 1,7-positions (Scheme 2).122–126
intensity can be considered as being due to the transformation 3.1.2 C–H activity and oxidative nucleophilic reactions.
of a radiative S1 state into a nonradiative S1 state. BODIPYs with no substituents at the a-pyrrole carbons (i.e.
the 3,5-positions) are prone to oxidative nucleophilic attack.
Substituents can be introduced in a single step under an oxygen
3. General synthetic methods atmosphere, based on the strength of their nucleophilicity
(Scheme 3).127–133 Metal-mediated C–H functionalization can
The synthesis methods and structural modification strategies that also be applied, and mono- or disubstituted dyes can be
have been used to shift the main absorption and emission bands to obtained.134–136 A water soluble, sulfonated BODIPY dye has
longer wavelengths will be briefly described. Three main approaches been prepared via this route in low yield.134
have been identified for the modification of the BODIPY structure 3.1.3 Condensation reactions with benzaldehyde derivatives.
through peripheral substitution. The BODIPY structure can also be 3,5-Methyl BODIPY substituents have long been known to be
modified through fused-ring-expansion of the pyrrole moiety and sufficiently acidic to participate in Knoevenagel reactions.137
aza-substitution at the meso-position (Scheme 1). Recent research has demonstrated that methyl groups at
the 1,7-positions can be almost as acidic as those at the
3.1 Peripheral substitution of the BODIPY core 3,5-positions.138 Tetrastyryl-substituted BODIPY derivatives can,
3.1.1 Nucleophilic and transition metal catalyzed cross coupling therefore, be obtained via condensation reactions of 1,3,5,7-
reactions. 3,5-Dichloro-BODIPY and other 3,5-dihalogenated tetramethyl-BODIPYs with aromatic aldehydes. The water that
BODIPYs are reactive towards aromatic substitution by oxygen, is formed as a byproduct can be removed by using a Dean–Stark
nitrogen, sulfur, selenium and tellurium nucleophiles,102–112 apparatus or dry molecular sieves. Usually, this reaction affords
and are also reactive in various transition metal catalyzed cross- mixtures of products. The relative yields of the mono- to tetra-
coupling reactions, such as Suzuki and Stille arylations, Heck styryl-substituted BODIPYs can be adjusted by modifying the
Scheme 1 General synthetic methods for red/NIR BODIPY derivatives.
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a tetravinyl configuration.140–142 Knoevenagel condensation

reactions with aromatic aldehydes have been identified as one
of the best strategies for obtaining red/NIR region absorbing BODIPY
derivatives that are suitable for use in applications such as labeling
reagents,143–146 energy concentration,147–161 photodynamic
therapy,162,163 molecular switching,164–167 chemosensors31,168–171
and laser dyes (Scheme 4).172–174
3.2 Aromatic ring fusion

3.2.1 Reactions of aromatic ring-fused pyrroles with aldehydes.

Aromatic ring-fused pyrroles can be synthesized through Michael
addition or Paal–Knorr reactions.175–179 The reaction of modified
pyrroles with aldehydes under acid-catalyzed conditions affords
dipyrromethenes, which can be oxidized with DDQ and coordi-
nated with a boron atom under alkaline conditions.43 Modified
pyrroles can be reacted with acid chlorides or anhydrides to directly
Scheme 2 The structural modification of 3,5-dichloroBODIPY via metal afford dipyrromethenes and BODIPY products with no DDQ
catalysis and nucleophilic substitution reactions. The R and Nu groups are oxidation step (Scheme 5).43,46,180,181
used to denote a wide range of different substituents. 3.2.2 Reactions of acylpyrroles with structurally modified
pyrroles. The synthesis of asymmetric BODIPY dyes has been
achieved via condensation of acylpyrrole 12 with a second
modified-pyrrole under Lewis acid catalyzed conditions,
followed by a reaction with an excess of base and BF3Et2O
(Scheme 6).182 Recently, it has been reported that dipyrro-
methenes can be prepared from a condensation reaction invol-
ving only the acylated pyrrole.183 This new route for forming
BODIPYs is a one-pot procedure. Since only facile purification
Scheme 3 Formation of a-substituted BODIPYs via metal-catalyzed C–H
steps are required and the products are obtained in good yield,
bond activation and oxidative nucleophilic substitution reactions.
this approach is likely to be increasingly used to form red/NIR
region dyes in future.
concentrations of the reactants, the amount of aromatic aldehyde
added, and the reaction time. When p-dimethylaminobenzaldehyde 3.3 Aza-substitution at the meso-position
is used, however, the reaction can be restricted to the mono- 3.3.1 Reactions of pyrroles with nitrosopyrroles. Aza-BODIPY
substituted compound.139 The methyl groups at the 1,3,5,7- dyes can be prepared by reacting a pyrrole with a nitrosopyrrole,
positions can be reacted in a stepwise manner, which enables followed by a reaction with BF3Et2O, either in a separate step or
the attachment of three different additional substituents in in situ, or by the formation of aza-dipyrrin structures from
Scheme 4 The condensation reaction of 1,3,5,7-tetramethyl-BODIPY with aromatic aldehydes.
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Scheme 5 Synthesis of BODIPY dyes through the reaction of pyrroles with aldehydes or benzoyl chlorides.
chalcones and nitromethane, or cyanide, followed by a condensation

reaction with ammonium acetate (Scheme 7). One-pot synthetic
routes to aza-dipyrrins have been known since 1943,184–186 but it was
not until 1994 that aza-BODIPY 17 was reported in the literature and
its remarkable spectroscopic properties were highlighted.187 In
recent years, aza-BODIPY dyes have been studied extensively by
the O’Shea research group.188–194 The key advantage of aza-BODIPY
dyes is that a marked red shift of the absorption and emission bands
Scheme 7 Synthesis of aza-BODIPY dyes via the reaction of a pyrrole
can be achieved without modifying the most important optical and with a nitrosopyrrole.
photophysical properties of BODIPY dyes, such as their high molar
absorption coefficients, narrow absorption and emission bands,
small Stokes shifts, and excellent photostability.
3.3.2 Reactions of phthalonitriles with arylmagnesium
bromides. Aza-dipyrrins can be prepared in moderate yield through
a one-pot reaction by reacting a phthalonitrile with 2.5 eq. of an aryl
magnesium bromide by steam distillation, followed by recrystalliza-
tion of the crude product from pyridine (Scheme 8).195 BF3Et2O Scheme 8 Synthesis of an aza-BODIPY dye via the reaction of a phthalo-
nitrile with aryl magnesium bromide.
can be used to convert the aza-dipyrrins into the corresponding
aza-BODIPY dye.196,197 This method, developed by the Shen,
Luk’yanets and Kobayashi groups, is both facile and commercially with 1 eq. of aryl magnesium bromide with no water steam
viable, since phthalonitrile is commercially available and aryl- distillation.198
magnesium bromides are easily prepared. A marked red shift
of the absorption and emission bands was observed relative to
the spectra of conventional 1,3,5,7-tetraaryl aza-BODIPY dyes.
The introduction of additional substituent groups on the precursors 4. Theoretical descriptions of the
is straightforward, so the spectral properties of the aza-BODIPY electronic structures of a series of
products can potentially be further fine-tuned. In recent studies, structurally-modified BODIPY dyes
aza-dipyrrins have also been obtained by reacting a phthalonitrile
The aim of this review is to examine the electronic structures of
different types of long wavelength absorbing BODIPYs to identify
the key trends observed in the spectral and redox properties and
in theoretical calculations, in a manner that will facilitate the
future rational design of red/NIR region BODIPY dyes with
properties suitable for specific applications. A series of eighteen
BODIPY derivatives have been selected for study by DFT and
TD-DFT, Fig. 5, so that the most important trends in the electronic
structures and optical properties can be clearly demonstrated. The
Gaussian 09 software package199 was used to carry out B3LYP200–204
geometry optimizations with SDD basis sets.205 The same approach
was then used to carry out TD-DFT for each of the optimized
structures, Fig. 5. The trends predicted in the HOMO–LUMO gaps
and in the energies of the main spectral bands are broadly
similar to that observed experimentally in the energy of the main
Scheme 6 Synthesis of BODIPY dyes through a reaction of acylpyrroles
absorption band. A detailed consideration of the alignments of
with another pyrrole (top) and through the condensation of only the the angular nodal patterns of the HOMO and LUMO can
acylated pyrrole (bottom). therefore be expected to provide insight as to why particular
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Fig. 5 The molecular structures for a series of BODIPY dyes selected to demonstrate trends in the energies of the HOMO and LUMO of the p-system
and hence in the magnitude of the HOMO–LUMO gaps and the wavelengths of the main spectral bands. The numbering used for each dye in the
remainder of the text is provided in each case.
structural modifications result in red shifts of the main spectral (iv) heteroatom substitution, (v) rigidization with fused-rings,
bands in a similar manner to the perimeter model approach (vi) fused-ring expansion of the p-system, (vii) b-aromatic ring-
developed by Michl to study trends in the optical spectra of fusion combined with a-substitution, (viii) the incorporation of an
aromatic and heteroaromatic cyclic polyenes.72–74 aza-nitrogen atom, (ix) formation of BODIPY dimers, and (x) core
modification to form BODIPY analogues.
5. Wavelength tuning strategies 5.1 Aryl-substituted BODIPYs
The effects of ten major structural modification strategies will The introduction of aryl substituents has proven to be an
be examined so that their relative effectiveness can be assessed: effective strategy for achieving a red shift of the main spectral
(i) aryl substitution, (ii) alkynyl substitution, (iii) styryl substitution, bands. The usefulness of this strategy will be explored by
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examining the properties of diaryl compounds with substituents of the pyrrole rings (Fig. 6), where there are large MO coefficients
at the 3,5-positions and of polyaryl compounds. (Fig. 3). Although the differing substitution patterns on the pyrrole
5.1.1 Diaryl-substituted BODIPYs. The absorption and rings and the electron withdrawing properties of the para-iodo
emission maxima of diaryl-substituted BODIPYs 21–34 are group on the meso-substituent make direct comparison with the
shifted to longer wavelengths, relative to those of the unsubstituted classic BODIPY structure of 51 problematic in this regard, it is
BODIPY 20.206 The bathochromic shift for 21 is approximately noteworthy that the para-electron-donating group of 22 results in
52 nm. A destabilization of the HOMO of 21 would normally be an even larger red shift.207,208 The introduction of ortho-methoxy-
anticipated since phenyl rings are incorporated at the 3,5-positions phenyl rings onto the BODIPY core at the 3,5-positions to form 23
Fig. 6 The angular nodal patterns of 1–18 (Fig. 5) at an isosurface value of 0.02 a.u. (top). The energies of the frontier p-MOs (bottom). Thicker lines with
diamonds and squares are used to denote the HOMO and LUMO. Blue circles and red diamonds are used to denote the predicted absorption band
energies and the HOMO–LUMO gaps. The trends observed in these values closely follow those of the observed absorption band energies that are
highlighted with larger green circles. The numbering used for each dye in the remainder of the text is provided in each case.
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results in a decrease in the molar extinction coefficient and fused-ring-expanded aromatic substituents to form 24–27 leads to a
FF value, and shortens the wavelengths of the maxima of the red-shift of the absorption and emission maxima and an increase
main absorption and emission bands.207,208 The incorporation of in the FF values.209 There is a 35 nm red shift of the absorption
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band compared to those of 24 and 25 based on a change of the maxima between 561–597 nm and 597–640 nm, respectively,
attachment position by one carbon atom. The relative orientations which are red-shifted by 70–120 nm compared to those of 20, the
of the indacene plane and the attached aromatic rings are deter- unsubstituted BODIPY dye.117,214–219 When the MO energies of
mined by the size of the substituent. When larger fused ring 35 are compared to those of a classic tetramethyl-BODIPY
systems are introduced at the 3,5-positions, the two p-systems dye such as 51 (Fig. 6) it is clear that the narrowing of the
cannot remain coplanar due to the constraints imposed by the HOMO–LUMO gap is due primarily to a stabilization of the
BF2 moiety. For example, 25 has been found to retain a higher level LUMO. This is probably related to the absence of the inductive
of co-planarity than 24.209 and mesomeric interactions between the BODIPY fluorophore
The spectral bands of 3,5-di(benzo[b]thiophen-3-yl)- and a meso-phenyl substituent. Any stabilization of the HOMO in
substituted BODIPY 28 lie at the same wavelengths as those this regard is cancelled out by the effect of incorporating phenyl
of 22, but it has a much higher FF value. This difference is groups as the 3,5- and 1,7-positions. Although the emission
related to the incorporation of a mesityl group at the meso-position maxima of 35–39 lie close to each other, significant differences
and the bulky benzothiophene moiety at the 3,5-positions, since are observed in their fluorescence quantum yields. Although 35
there is no free rotation of the substituents and this limits the rate of and 38 have extremely high FF values, those of 36, 37 and 39 are
nonradiative decay. In the solid state, the spectroscopic properties of only moderately high. The difference is probably due to the
28 are close to those observed in solution, due to weak intermole- presence of phenyl groups at the meso positions, since the
cular interactions.210 The 3,5-di-(benzothiazolyl)-substituted BODIPY conformational flexibility that is caused by the steric congestion
29 has an intense emission band at 643 nm with a high FF value that can be expected to accelerate the rate of nonradiative decay. The
is insensitive to solvent polarity.211 There is a 67 nm red-shift of the incorporation of electron-donating OMe groups into the structure
band maxima of 30 when compared to those of 21. These spectral of 40 results in only small bathochromic shifts compared to the
differences can be best explained in terms of differences in the maxima observed for 39. This indicates that there is only a weak
degree of steric hindrance upon changing from a 6- to a 5-membered interaction between the peripheral phenyl groups and the indacene
ring. The electronic properties of thiophenes are similar to those of plane. X-ray structures revealed that the molecules adopt distorted
para-methoxy-phenyl rings.212 and ‘‘propeller-like’’ conformations (Fig. 7).218,219 39 and 40 are
Modifications at the meso-position usually do not influence brightly fluorescent in the solid state. The distorted conformations
the position of the absorption and fluorescence emission probably inhibit exciton coupling effects associated with inter-
bands, since there is normally little scope for a mesomeric molecular aggregation.217,218
interaction between aryl substituents and the BODIPY chromophore.
However, the incorporation of a strongly electron-withdrawing CF3 5.2 Alkynyl-substituted BODIPYs
substituent at the meso-position in the structures of 31 and 32 causes Significant red shifts of the main spectral bands can also be
a large ca. 35 nm bathochromic shift relative to the main spectral obtained by introducing peripheral alkynyl substituents. A
bands of the aryl-substituted 21 and 30 dyes.213 There is a marked small Stokes shift is observed for the spectral bands of the
stabilization of both the HOMO and LUMO of 31 (Fig. 6) due to the 1,7-dialkynylphenyl substituted dye 41 and there is a very high
inductive effect associated with the electron withdrawing CF3 group. FF value of 1.00.122 The spectral bands of 41 lie at similar
The narrowing of the HOMO–LUMO gap that leads to the red shift wavelengths to those of the 2,6-disubstituted dye 42 and are
of the main absorption band is related to there being a larger blue-shifted in comparison to those of the 3,5-disubstituted dye
stabilization of the LUMO, which has a large MO coefficient on 46. The probable reason is that the HOMO has smaller MO
the meso-carbon, due to a mesomeric interaction related to hyper-
conjugation. 31 and 32 have high FF values and are likely to have at
least two advantages in the context of biochemical probe applica-
tions. Firstly, the relatively small size of 31 and 32, and secondly, the
usefulness of the CF3 group as an NMR marker.213
The bathochromic shifts observed after diaryl substitution
at the 1,7-positions to form 33 and 34 are not as large as those
observed for the corresponding 3,5-disubstituted dyes.122
The absorption and fluorescence emission maxima of 34 are
blue-shifted by about 74 and 72 nm, respectively, relative to
those observed for its 3,5-dithiophene BODIPY analogue 30.
The 1,7-disubstituted dye 33 has similar spectroscopic properties
to its 3,5-diphenyl analogue 21 with blue-shifts of ca. 17
and 39 nm, respectively. The smaller effects observed when
substituents are introduced at the 1,7-positions seem to be
attributable to the HOMO having smaller MO coefficients at
the 1,7-positions, Fig. 3.122
5.1.2 Polyaryl-substituted BODIPYs. Polyphenylated BODI- Fig. 7 X-ray structure of 39. (Reprinted with permission from ref. 218.
PYs 35–39 have intense absorption and fluorescence bands with Copyright r 2011 American Chemical Society.)
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coefficients at the 1,7-positions (Fig. 3).122 Dyes 42 and 43 have band associated with a low-lying charge-separated excited state.
donor–p-bridge–donor structures. This results in high two Negligible fluorescence is observed due to a charge transfer
photon absorption cross sections and strong emission in the interaction between the ferrocenyl donor group and the boron-
red region. There is an increase in the Stokes shift and the dipyrromethene moiety.225 The red-shifts of the main spectral
width of the main fluorescence band on moving from 42 to 43. bands of arylethynyl BODIPYs 48–50 are significantly larger.116
This behavior is consistent with the formation of a low-lying Interestingly, the presence of 2-ethynylthiophenes in the structure
charge separated S1 state, prior to emission.220,221 44 contains of 48 causes larger red-shifts of the spectral bands than those
two dimesitylboryl (Mes2B) moieties and exhibits intense observed for 49, a 3-ethynylthiophene substituted BODIPY.116
orange-red fluorescence with a FF value of 0.65 in CH2Cl2
solution. 44 can be used as a ‘‘turn-off’’ fluorescent probe for 5.3 Styryl-substituted BODIPYs
F, since binding of F by the Mes2B moieties results in a Styryl substituents have proven to be a particularly useful
nonradiative PET deactivation pathway.222,223 strategy for forming red/NIR region BODIPY dyes. The properties
The introduction of bulky triphenylsilylphenylethynyl of mono-, di-, multi-p-, and meso-p-styryl and meso-vinyl sub-
groups to form 45 results in solid-state fluorescence at stituted BODIPYs will be examined in depth, so that their
613 nm with a quantum yield of 0.03, which is lower than the properties can be compared.
value for the corresponding monosubstituted BODIPY (0.07), 5.3.1 Monostyryl-substituted BODIPYs. When a styryl sub-
most likely due to the enhanced probability of internal conversion stituent is introduced to obtain 52 from 51,226 the absorption
caused by electronic coupling between the triphenylsilylphenyl maximum shifts by ca. 60 nm into the red region of the visible
ethynyl moiety and the BODIPY core.224 However, more intense spectrum.173 When strongly electron-donating –NMe2 groups
solid-state emission (FF = 0.25) is observed for monotriphenyl- are introduced at the para-positions of the phenyl ring to form
silylphenyl BODIPY, which suggests that the introduction of the 54, the absorption maximum is shifted to the red by a further
bulky arylsilyl group is an effective way to enhance the solid- 34 nm.227 The band maximum observed when weakly electron-
state emission of BODIPY dyes.224 The 3,5-dialkynylphenyl donating –OH groups are introduced in 53 is almost
substituted BODIPY 46 absorbs and emits in the red region unchanged, however.228 The fluorescence emission maximum
(614 nm), unlike 42, the corresponding 2,6-disubstituted dye of 54 lies at 731 nm in polar solvents such as acetonitrile, due to
(573 nm).108 The fluorescence quantum yields of 46 are extremely a CT band associated with the dimethylamino group as the
high (FF = 1.0) and independent of solvent polarity.108 BODIPY 47 electron donor and the BODIPY core as the electron acceptor.
has an intense blue color in toluene due to the presence of two Protonation of the –NMe2 group eliminates this CT process and
absorption peaks. This has been attributed to the presence of a results in a blue shift of the absorption and emission bands to
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555 and 565 nm. The protonated species have high fluores- of the aryl group.231,232 The merocyanine conjugated dye 59
cence quantum yields, similar to those of 52.227 Generally, as is displays a further large bathochromic shift to ca. 650 nm due
obvious when the spectra of 54 and 55 are compared, varying to the extension of the p-conjugation system.233 Unfortunately,
the substituent group at the meso-position has only a minor the basic optical properties of this dye, such as the FF value and
impact on the absorption spectra and there are only very minor the absorption and emission spectra, have not been investigated
effects on the properties of the S1–S0 fluorescence band. The in detail. The incorporation of fluorene and indene rings with a
first protonation of 55 is at the virtually decoupled dimethyl- vinyl spacer to form 60 and 61 leads to a large red-shift of the
amino group of the meso-substituent, followed by protonation main spectral band, but the FF values differ markedly.234 The FF
at the dimethylamino group of the styryl fragment.139 value for 60 is very low (F o 0.02), and no significant increase is
When the phenyl moiety is changed to a pyrene to form observed in viscous solvents. This is probably due to the effect of
56,229,230 the extension of the p-conjugation system results in a nonradiative decay associated with the indene group. Theoretical
red-shift of the absorption and emission bands by 38 and 49 nm, calculations have confirmed that the efficient nonradiative
respectively, relative to those of 52. As would be anticipated, relaxation is caused by conical intersections between the S1
extending the p-conjugation system with electron-rich imidazole singlet excited state and the ground-state.234
and pyrrole rings through an ethenyl linker at the 3-position to 5.3.2 Distyryl-substituted BODIPYs. When two styryl sub-
form 57 and 58 results in a bathochromic shift which can be stituents are introduced at the 3,5-positions to form 62, a
further fine-tuned by modifying the electron donating properties narrow and intense absorption band is observed with a
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maximum at 629 nm.235,236 This represents a red-shift of of the pyridyl groups.237 Only moderate bathochromic shifts are
129 nm relative to that of 51, which has a conventional BODIPY observed in the spectra of 65 and 66, the 2,6- and 1,7-distyryl-
structure. The substitution with electron-donating dimethyl- substituted BODIPY analogues of 62.71,122 It is worth noting
amino groups at the para-positions of the phenyl rings of the that large Stokes shifts and low FF values are observed for
styryl substituents to form 63 shifts the emission band to the 2,6-distyryl substituted dyes. This is probably related to greater
NIR region.237 The use of this dye for probe applications has conformational flexibility of the molecular geometry in the
been investigated. pH-dependent absorption and fluorescence excited state, which increases the rate of nonradiative decay.71
changes have been observed at the blue end of the visible The iodine atom at the para-position of the meso-phenyl group
region due to the presence of two different protonation of 67 appears to have almost no effect on the photophysical
states.237 The main absorption band of pyridyl-substituted properties, since the photophysical values reported are almost
dye 64 lies at 620 nm and is further red-shifted upon addition the same as those of 62.238 The optical spectra of the bis-
of TFA due to a decrease in the electron-withdrawing properties anthracene derivative 68 contain broad and featureless bands
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and this dye has a low FF value. The two fluorophores of 68 5.3.3 Multi-p-styryl-substituted BODIPYs. By fine-tuning
remain in electronic isolation but display fast intramolecular the Knoevenagel condensation reactions of the four methyls
energy transfer.238 This differs from what has been reported for on the BODIPY core of 51 with aromatic aldehydes, it is
BODIPY–anthracene energy-transfer cassettes with linking alkynyl possible to obtain not only the monostyryl dye 52, but also
moieties.126,239 Marked red-shifts are observed for the spectral the di-, tri-, and tetrastyryl derivatives 77–79.138 In DFT calcula-
bands of 69 due to the extension of the p-conjugation system. tions (Fig. 6), there is a marked destabilization of the HOMO of
The higher-energy absorption bands at ca. 430 nm are probably 62 (which is very similar to 77), since the large MO coefficients
associated primarily with the pyrene moiety (Fig. 8).238 at the 3,5-positions enhance the mesomeric effect of the styryl
When the spectral data for 70 and 71, which have 5-membered substituents (Fig. 3). The absorption peak of 51 is shifted
heteroaromatic substituents at the 3,5-positions, are compared stepwise from 500 nm to 645, 665, and 689 nm in the spectra
with those for 62 which has phenyl rings, it is found that the of 77–79 in CHCl3, and the emission bands are shifted to 660,
incorporation of 3,5-difuranylvinyl substituents leads to a bath- 682, and 710 nm. This is especially noteworthy, since there are
ochromic shift of 42 nm, while a shift of 28 nm is observed for red-shifts of ca. 150, 172, and 200 nm relative to the emission
3,5-dithiophenevinyl substituents. This can be attributed to a band of 51. These dyes have very large molar absorption
narrowing of the HOMO–LUMO gap due to enhanced delocaliza- coefficients rivaling those of cyanine dyes. In addition to their
tion of the p-electrons in furan rings relative to thiophenes.212,240 facile functionalization and derivatization, the moderately high
The introduction of ferrocene moieties to form 72 results in a FF values make these styryl-BODIPYs strong candidates for use
large red-shift of 71 nm relative to the main absorption band of in dye applications.138
the phenyl substituted structure of 62. The compound is not It is interesting to note that when electron withdrawing
emissive, however, since there is substantial charge transfer formyl groups are introduced at the 2,6-positions, Knoevenagel
from the electron-rich ferrocene moiety to the main BODIPY reactions can only be initiated at the 7- or 1,7-positions.141
p-system.241 Similarly, no fluorescence is observed for meso- Steric hindrance prevents the Knoevenagel reaction from occur-
ferrocene substituted BODIPYs.225,242 The a-substituted struc- ring at the 5- or 3,5-positions, resulting in the formation of the
tures of 73 and 74 result in spectra with typical BODIPY 2,6-diformyl-1,7-distyryl-BODIPY 80. It should be noted that the
characteristics, such as narrow absorption bands with large formation of vinyl bonds at the 7-, and 1,7-positions facilitates
molar extinction coefficients (4120 000 M1 cm1).136 The further Knoevenagel reactions at the 3, and the 3,5-positions, to
emission maximum of 74 is shifted to 651 nm with a relatively form 2,6-diformyl-1,3,7-tristyryl- and 2,6-diformyl-1,3,5,7-
high FF value. In the case of b-substituted BODIPY dyes 75 and tetrastyryl-BODIPYs 81 and 82. In CH2Cl2, BODIPYs 80–82 have
76, the main absorption and emission bands also exhibit sub- intense absorption bands at 576, 634 and 688 nm, respectively,
stantial red-shifts, but the bandwidths become broader and with emission bands at 673, 686 and 722 nm. The significant
there is a decrease in the molar extinction coefficients to around red-shifts are caused by the extension of the p-conjugation
60 000 M1 cm1. 76 has a FF value of only 0.054 and thus has systems. Formyl-BODIPY dyes have lower FF values than con-
properties that are not as favorable for many applications as those ventional BODIPY dyes. This suggests that the presence of
of the corresponding a-substituted BODIPYs. When compared to formyl groups quenches the fluorescence. The trends observed
the spectra of dyes substituted at the 3,5-positions, the absorption for 80–82 confirm again that the incorporation of styryl groups
band of the 2,6-substituted 76 dye are blue-shifted and the emis- at the 3,5-positions has a larger effect on the wavelength of the
sion bands are red-shifted. This is related to the larger Stokes shifts main absorption band than incorporation at the 1,7-positions.
that are observed for 2,6-substituted BODIPYs.136 A red-shift of 50–60 nm is observed upon the incorporation of
each styryl substituent at the 3,5-positions, while a 20–30 nm
shift is observed for each 1,7-position substituent.141 The meso-
(thiophen-2-yl)quinoline appended BODIPY 83 has an absorp-
tion maximum at 708 nm that does not shift when the solvent
polarity is increased.243 A large pseudo-Stokes shift of up to
400 nm is observed for the energy-transfer cassette that is
formed due to efficient through-bond energy transfer of up to
99%. 83 can also selectively bind Fe(III) ions in aqueous solution
and in living cells, so this demonstrates the potential
for developing chemosensors based on through-bond energy
transfer cassettes that contain the BODIPY fluorophore as an
electron acceptor.243 The preparation of the tetrastyryl-
substituted BODIPY 79 with four methoxy substituents at the
para positions enables the synthesis of dyes with different
substituents, such as 84.140,142 These highly colored dyes
Fig. 8 Absorption spectra recorded for a series pyrene-substituted BOD-
IPY dyes in MTHF. The spectrum of 69 is shown in gray. (Reprinted with
display outstanding optical properties with the absorption
permission from ref. 238. Copyright r 2010 Wiley-VCH Verlag GmbH & maxima shifting to 700 nm for 84 in dioxane, which was selected
Co. KGaA, Weinheim.) to limit aggregation effects and the rate of photodegradation.
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The FF value of 79 is 0.34, but decreases to 0.13 for 83, due to the more readily and efficiently than those with no substituents at
presence of the dimethylaminophenyl moieties. these positions. The absorption band maxima of 85 and 86 are
When a Knoevenagel reaction is carried out for a tetramethyl shifted dramatically to the red to lie at 732 and 797 nm in
BODIPY derivative with 4-t-butylphenylethynyl substituents at CHCl3, respectively, while the emission band maxima lie at 756
the 2,6-positions, tetrastyryl BODIPYs 85 and 86 are formed.138 and 835 nm. High molar absorption coefficients similar to
BODIPYs with substituents at the 2,6-positions tend to react those of 67–69 have been reported. Although a moderate FF
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value of 0.23 is observed for 85, the quantum yield of 86 decreases to form 95, the HOMO and LUMO are mostly localized on the
markedly to 0.05 in CHCl3, due to strong charge transfer character BODIPY and meso-styryl moieties, respectively, in a manner that
in the S1 state caused by the p-N,N-dimethylaminostyryl moieties.138 could facilitate the injection of an electron into the conduction
5.3.4 meso-Vinyl substituted BODIPYs. meso-Vinylic BODI- band of TiO2 in solar cell applications (Fig. 9).245
PYs are weakly fluorescent, particularly in polar solvents,
probably due to conformational flexibility associated with the 5.4 Heteroatom substituted BODIPYs
meso-vinyl groups. The polymethine-structure of 88 results in a The main absorption and emission bands of 3,5-position hetero-
red-shift of ca. 127 nm relative to the absorption band of 87. An atom substituted BODIPYs 96–100 have a similar morphology to
extension of the polymethine chain to form 89 leads to a further those of classic BODIPYs (Fig. 4 and 10).104,105,109 On moving
100 nm red-shift of the absorption maximum.244 from substituents with linking oxygen atoms, to those with
Interestingly, the main absorption bands of polymethine- nitrogen, sulfur, and selenium atoms and then to those with
substituted BODIPYs 88–90 are no longer observed upon proto- tellurium atoms, the absorption and emission spectra display a
nation and a new peak gains intensity at shorter wavelength. No red-shift from the green to the NIR region. The extent of the red-shift
fluorescence is observed for these protonated species.244 In contrast is related to the electron donating properties of the heteroatom. The
with what is observed upon substitution at the 3,5-positions, there is positions of the absorption and emission maxima depend to a
almost no shift observed in the main absorption band of meso-styryl minor extent on the solvent polarity. A red-shift of less than 10 nm is
dyes 92–93 and the vinylic thioether 94.245,246 Theoretical calcula- observed on moving from toluene to THF. This can be attributed to
tions have revealed that when 92 is further reacted with an aldehyde the difference in solvent polarizability and a decrease of the dipole
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intensity and results in a marked blue-shift in its band maximum. It

has recently been reported that these spectral changes can be used
as a sensor for HOCl in living cells.247
5.5 Fused-ring systems

Free rotation of aryl-substituents at the 3,5-positions tends to
limit the extent of the red-shift of the main spectral bands.
Various strategies have been adopted to achieve a greater degree of
co-planarity between the p-systems of the aryl substituents by

forming rigidized fused-ring systems with sp3 hybridized carbons,
heteroatoms and through B–O chelation. The properties of each of
these types of BODIPY dyes will be examined in depth.
Fig. 9 (a) HOMO and (b) LUMO of 95 calculated by DFT. (Reprinted with 5.5.1 Fused-ring systems with sp3 hybridized carbons.
permission from ref. 245. Copyright r 2011 American Chemical Society.) When the conformational rigidization of phenyl rings substituted
at the 3,5-positions is achieved by incorporating sp3 hybridized
carbons, the free rotation of the phenyl rings is eliminated. This
moment in the excited state with respect to the ground state. The FF leads to an increase in the FF value and the molar extinction
value of 100 is only 0.01 in THF, which is markedly smaller than coefficient of the main absorption band. There is a marked red-
those of other heteroatom-substituted BODIPYs. The main pathway shift of the absorption maximum, due to a narrowing of the HOMO–
responsible for this is ISC to the triplet manifold due to the heavy LUMO gap of 102 relative to that of 21 (Fig. 6), which is predicted to
atom effect. Charge transfer from the electron rich Te atoms to the be caused by a relative destabilization of HOMO, since there is a
relatively electron deficient BODIPY core also causes fluorescence larger mesomeric interaction between the phenyl groups and the
quenching in the case of Te-BODIPYs.105 When a sulfur-atom is BODIPY core. The presence of methyl groups at the 1,7-positions of
introduced at the 2-position to form 101, the absorption band 103 prevents the free rotation of the meso-aryl ring, leading to an
maximum lies in the same region as that of classic BODIPY dye increase in the quantum yield relative to 102.208,248 Surprisingly, the
51 and there is a broad emission band in the red region with an maximum of the absorption band of the half-oxidized BODIPY 104 is
unusually large Stokes shift of 137 nm.247 The strong solvent not red-shifted relative to 103, but the fluorescence emission is red-
dependence of this emission band indicates that the S1 state has shifted by 21 nm. The extinction coefficient and quantum yield for
significant charge transfer character. Oxidation of the thioether to the main absorption band of 104 are less than half of those of 103,
form an electron-withdrawing sulfoxide restores the fluorescence despite the extension of the p-conjugation system.248
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The meso-hydroxyquinoline fragment of dye 105 can be used modified by the introduction of styryl groups at the 3,5-positions
as a NIR region chemosensor for metal ions.249 BODIPYs 106 to provide NIR region chromophores that are suitable for
and 107 absorb and fluoresce in the red region with a slight red- applications.250 Two different orientations are possible for the
shift of the band maxima with respect to 102 and 103, indicat- fused dihydronaphthalene rings with respect to the core indacene
ing a weak conjugation effect at the 1,7-positions.122 The plane.250 The rigid structure of 110 contains two spirofluorene
introduction of bridged phenyl groups at the 1,7-positions, so moieties. This leads to a significant bathochromic shift of the
that a fused dihydronaphthalene group is formed at the b fluorescence emission. A high FF value is retained, since the
position of the BODIPY core to form dyes 108 and 109, leads spirofluorene moieties increase the rigidity of the structure, thereby
to a blue-shift of the absorption and fluorescence emission reducing the rate of nonradiative decay.251,252 The combination of
maxima compared to the values reported for dye 102 con- the extended p-conjugation system and the rigid conformation of
strained at the 3,5-positions.250 This confirms again that the 111 leads to a further red-shift, along with a decrease in the FF
introduction of substituents at the 3,5-positions has a larger value and the molar extinction coefficient.253
effect on the absorption maxima than the introduction of 5.5.2 Fused-ring systems with heteroatoms. Rigid confor-
substituents at other positions. 108 and 109 could be further mations can also be achieved with a benzofuran moiety as is
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the case with 112 and 113.130,248 These have more intense the analogous unconstrained 21 dye. The most prominent difference
absorption and fluorescence bands at longer wavelengths than between the 2,6-dioxy-benzofuran 113 and the 3,5-dioxy-benzofuran
112 is that there is a larger red-shift of the absorption and emission
bands of 113, with bands which lie 50 nm to the red of those of 112
due to the enhanced p-conjugation of the 2,6-dioxy derivatives.
Recently, a new series of analogues named Keio Fluors
114–118 were prepared with structures similar to those of
classic BODIPYs but with furan ring moieties fused at the
2,6- and 3,5-positions. These dyes have extremely high molar
extinction coefficients, FF values, and brightness compared to
other constrained systems.23,254 In DFT calculations (Fig. 6), the
energy of the HOMO of 115 is similar to that of 51, a classic
BODIPY dye, but there is a large stabilization of the LUMO due
to the absence of an electron-donating aryl-substituent at the
meso-position and/or the bonding interactions with the oxygen
atoms that are predicted at the points of attachments of the
fused furan rings. Keio Fluors 114–118 can be viewed as being
Fig. 10 The absorption spectrum of 97 measured in a wide range of
3,5-distyryl substituted BODIPY with oxygen atom bridge linkers
different solvents. (Reprinted with permission from ref. 109. Copyright r that hinder the free rotation of the ethenyl fragments. These dyes
2009 American Chemical Society.) fluoresce in the NIR region with high quantum yields (Fig. 11).
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Fig. 11 The absorption and emission spectra of, from left to right, 1,3,5,7- Fig. 13 Normalized absorption (solid line) and emission (dashed line)
tetramethyl-BODIPY and a series of Keio Fluors (KFL1–4) measured spectra of 122 (green) and a related tribrominated structure (red) in
in CHCl3. (Reprinted with permission from ref. 23. Copyright r 2008 CH2Cl2. (Reprinted with permission from ref. 256. Copyright r 2013 Royal
American Chemical Society.) Society of Chemistry.)
The main absorption band of the methyl substituted structure of When the conformations of BODIPY dyes are constrained by
114 is slightly blue shifted relative to that of the benzofuran 112 sulfur atoms, such as with dyes 119–122,255,256 slight red-shifts
and there is a very small Stokes shift. Overall, the emission of of the main spectral bands are observed and, with the exception
115 is red-shifted by 151 nm compared to that of 51, the classic of 119,248 there is a decrease in the FF value, but not the molar
tetramethyl-BODIPY dye. There is a further red-shift of ca. 20 nm extinction coefficient, relative to the corresponding oxygen
due to the introduction of electron-donating methoxy- atom constrained dyes. A further red-shift of 108 nm was
substituents at the para or ortho-positions to form 116 and observed when thienyl groups were attached to the benzothio-
118. According to previous reports (from 22 to 23), the presence phene rings to form 122 (Fig. 13). Bromine atoms have been
of ortho-methoxyphenyl rings at the 3,5-positions of the BODIPY incorporated into the structures of 121 and 122 to enhance the
core tends to have a negative effect on the optical properties, rate of ISC and hence the singlet oxygen quantum yields,
since there is a shortening of the wavelength of the spectral making these BODIPYs potentially suitable for use as NIR
bands, and a decrease in the molar extinction coefficients and region photosensitizers.255,256
FF values. However, the ortho-methoxyphenyl-substituted 118 5.5.3 Fused-ring systems with B–O chelation. The absorption
dye exhibits similar characteristics to other Keio Fluors type bands of O-chelated BODIPYs exhibit a significant red-shift of
dyes, since there is no scope for hindered rotation of the phenyl ca. 65–80 nm. Narrow emission bands are observed and there is
ring. This means that fine tuning of the absorption and emission an increase in the FF values relative to the corresponding precursor
band maxima can be achieved for this series of dyes by attaching dye (i.e. 123 and 124, or 127 and 128). This is probably due to a
substituents at various positions on the phenyl ring. The photo- decrease in the dihedral angle between the phenyl rings and the
physical properties can be attributed to the benzofuran moiety BODIPY core. When the MO energies of 124 are compared to those
and the phenyl rings being coplanar. This has been confirmed by of 21 (Fig. 6), which has freely rotating phenyl rings, it is clear that
single-crystal X-ray crystallography (Fig. 12).23,254 A significant the narrowing of the HOMO–LUMO gap is mainly due to a
bathochromic shift of ca. 50 nm is observed for the main spectral destabilization of the HOMO when the aryl substituents are con-
bands of 117, compared to those of 115 due to the presence of a strained to lie almost co-planar with the BODIPY core.257,258 The
meso-CF3-substituent, for reasons similar to those described chiral boron center in the mono O-linked structure of 125 could be
previously for the spectra of 21 and 31, and for 30 and 32. used in chiral recognition applications or to provide circularly
polarized luminescence.259,260 The bicyclo[2.2.2]octadiene-fused
(BCOD-fused) and O-chelated dye 128 exhibits unusually strong
fluorescence with a FF value of 0.99. This can be attributed to the
BCOD rings blocking the quenching associated with p–p stacking
of the BODIPY core, the absence of rotation of a meso-phenyl group
and the B–O chelation of the phenyl rings at the 3,5-positions.258
5.6 Fused-ring-expansion systems
Fig. 12 The front and side views of the X-ray molecular structure of 117.
Another strategy that has proven to be useful in producing NIR
(Adapted with permission from ref. 254. Copyright r 2009 Wiley-VCH BODIPY dyes is fused-ring-expansion of the p-system. Fusion
Verlag GmbH & Co. KGaA, Weinheim.) can be achieved at either the b-positions of the pyrrole ring or at
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the a-position, and BODIPY moieties have also be fused with

porphyrin macrocycles.
5.6.1 Fused-ring-expansion at the a and b-positions. BOD-
IPY 129 contains two fused BCOD moieties at the b positions
and has a spectrum similar to that of tetramethyl-BODIPY 51
with a high FF value of 0.81.261,262 Fused-ring-expansion of the
BODIPY structure to form BODIPYs 129–139 results in spectral
bands that are bathochromically shifted into the red end of
the visible region and in some cases into the NIR region.
For example, the absorption bands of 130–133 exhibit large Fig. 14 The effect of fusion of a benzene ring at the a-position on the
bathochromic shifts of 71, 42, 96, and 131 nm, respectively, energies of the frontier p-MOs of 131. (Reprinted with permission from
relative to the main absorption band of 129. In DFT calcula- ref. 263. Copyright r 2013 Royal Society of Chemistry.)
tions (Fig. 6), there is a marked destabilization of the HOMO of
130 relative to that of 51, a classic BODIPY dye, due to the
antibonding nature of the interactions with the fused benzo on the energy of the HOMO (Fig. 14). In contrast, benzo-fusion
groups at the points of attachments on the b-carbons of the at the b-positions destabilizes the HOMO, but has a smaller
pyrrole moieties. The absorption and emission spectra of the impact on the energy of the LUMO (Fig. 14). These results can
benzo[b]-fused BODIPY 130 exhibit similar band morphologies be conceptualized by viewing the BODIPY structure as a combi-
to those of classic BODIPY dyes (e.g. narrow bandwidths, nation of an electron-donating pyrrole and an electron-accepting
mirror-symmetry with the emission band) and retain high FF azafulvene moiety. The benzo[a]-fused structure enhances the
values.262 However, the benzo[a]-fused BODIPY 131 lacks these azafulvene character resulting in a stabilization of the LUMO
typical BODIPY properties. A broad absorption band (500– energy level, while the fusion of a benzene ring at the b-positions
700 nm) is observed and there is no emission intensity, enhances the pyrrole character, resulting in a destabilization of the
probably due to conformational flexibility associated with the HOMO.263,264 In the 1980s, the benz[c,d]indole 132 was reported to
steric hindrance between the aryl substituents.263 have an absorption band at 622 nm, but the emission spectrum is
Interestingly, DFT calculations and electrochemical analyses not available and no quantum yield values are available.265 There is
indicate that the fusion of a benzene ring at the a-position a particularly large red-shift of the spectral bands when acenaphtho
results in a stabilization of the LUMO but has a smaller effect groups are fused at the b-carbons of the pyrrole moieties to form
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133.266 There is a significant stabilization of the LUMO (Fig. 6), decoupled architecture of meso-aryl-substituted BODIPYs with
since there is a bonding interaction at the points of attachment on large torsion angles between the phenyl ring and the BODIPY
the b-carbons of the pyrrole moieties. There is also a destabilization core. There is a smaller stabilization of the LUMO of 134 than
of the HOMO, since there is an antibonding interaction at the for 133 (Fig. 6), possibly due to a weaker bonding interaction at
points of attachment of the acenaphtho rings. the points of attachment of the peripheral fused rings on the
The phenanthro-fused BODIPY 134 has an intense absorp- b-carbons of the pyrrole moieties. The decrease in the HOMO–
tion band at 630 nm with a high molar absorption coefficient LUMO gap causes a slight blue shift of the main absorption
(e Z 100 000) and a FF value that is near unity.267 This suggests band, so incorporating acenaphtho groups appears to be a
that the fusion of the larger phenanthrene moieties induces a better strategy for achieving a red shift of the main spectral
‘propeller-like’ distortion of the BODIPY structure (Fig. 15), bands. It should be noted, however, that the absorption band of
which facilitates a stronger electronic influence by the meso- 134 lies in the output range (ca. 635 nm) of the most commonly
substituent while retaining the advantages of the virtually used red light excitation sources (HeNe and diode lasers).
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solid state.268 The naphthobipyrrole derived BODIPY 136 has

markedly red shifted absorption (727 nm) and emission band
maxima (744 nm).269 The absorption band has a very high
molar extinction coefficient (e = 327 000 M1 cm1) and there is
a reasonably high FF value. The dye was also found to have
reasonably good photostability. The emission peaks for dyes
137 and 138, which contain a single fluorantho[8,9-f ]isoindole
moiety and either a benzo or acenaphtho fused ring, are
observed at similar wavelengths, while the absorption bands lie
at 681 and 658 nm, respectively.270 When two fluorantho[8,9-f ]-

isoindole moieties are incorporated to form 139 the main spectral
bands lie in the NIR region beyond 750 nm and there is a
relatively low FF value of ca. 0.3. 139 is unstable in air, probably
due to a large destabilization of the HOMO energy level, which
leads to a marked decrease in the first oxidation potential.270
5.6.2 meso-, b- and porphyrin-fused-BODIPYs. Another
strategy for achieving a bathochromic shift of the main BODIPY
absorption band is the fusion of the BODIPY p-system to the
Fig. 15 Crystal structure of 134 viewed from the top (A) and along the meso- and/or the b-pyrrole carbons of a porphyrin ring. This
B(1)–C(8) axis (B). (Reprinted with permission from ref. 267. Copyright r results in a marked expansion of the p-conjugation system and
2008 American Chemical Society.) a shift of the absorption and emission bands to the far-red of
the visible region or the NIR region. In contrast to classic
BODIPYs, 140 exhibits a broad envelope of absorption intensity
between 500 and 930 nm with maxima at 658, 784 and
867 nm.271 When an anthracene moiety is fused to the b-
positions of the BODIPY core, there is a remarkable bath-
ochromic shift of the absorption and emission (924 nm) bands,
but the FF value is under 0.008.271 In a similar manner, the b-
fused structure of BODIPY 141 results in a red-shift of the main
absorption band to 670 nm (e = 91 000 M1 cm1) together with
a shoulder at ca. 780 nm. Two distinct emission bands are
observed in a wide range of solvents at 742 and 830 nm. A
relatively low FF value of 0.008 was reported in toluene.272
Although this is mainly attributable to the effect of aggregation
in solution, other factors such as changes in conformation and
the charge transfer character of the S1 state (from the electron-
donating N-annulated perylene moiety to the electron-
accepting BODIPY core) may also contribute to the decrease
in the FF value.272
In compounds 142–144,273,274 BODIPY moieties are fused to
Fig. 16 The absorption spectra of 142 (solid line) and its Zn(II) complex
porphyrin rings. These dyes have intense absorption bands in
(dashed line) in CH2Cl2 at room temperature. (Adapted with permission
from ref. 273. Copyright r 2004 Elsevier.) the NIR region due to the extension of the p-conjugation
system. The absorption spectrum of 142, which has a BODIPY
moiety fused at the b-pyrrole carbons of a tetraphenylporphyrin
The properties of the chromophore can be fine-tuned through ring, contains four moderately intense bands in the 300–
further structural modifications. Styryl groups can be intro- 750 nm region, at 388, 413, 531, and 640 nm in CH2Cl2
duced at the 3,5-positions, leading to significant red-shifts of (Fig. 16). The emission maximum shifts dramatically to
the main spectral bands.267 BODIPY 135 has a more intense 693 nm and there is a low FF value of around 0.04. In 143, a
and red-shifted absorption band (673 nm) than that of 134. BODIPY moiety is fused to a meso-carbon and two neighboring
There is a higher relative stabilization of the LUMO of 135 b-pyrrole carbons of a Ni tetraarylporphyrin resulting in an even
(Fig. 6), due to the different points of attachments on the greater extension of the p-system and a larger bathochromic
pyrrole moieties. The FF value is relatively high, despite the shift to 890 nm (Fig. 17). When a second BODIPY moiety is
narrow HOMO–LUMO gap. The molecular structure of 135 is fused to form 144 there is a further shift of the absorption band
planar due to the absence of a steric interaction with a meso- to beyond 1000 nm, the longest wavelength to be reported for
aryl-substituent. Strong p–p interactions through the peripheral the absorption maximum of a BODIPY derivative (Fig. 17).
phenanthrene moieties leads to fluorescence quenching in the Although the fusion of the BODIPY chromophore to a
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This is the norm for Ni(II) porphyrins, however, due to the

presence of low-lying ligand-to-metal charge transfer bands.274
5.7 b-Aromatic ring-fused and a-substituted BODIPYs

Since b-aromatic ring fusion has been proven to be an efficient
way to shift the absorption and emission bands to longer
wavelength, structural modification at the a-positions provides
an opportunity to obtain a further bathochromic shift. For
example, when a phenyl group is introduced to form 145, a
very intense absorption band is observed at 634 nm in
CH2Cl2.275 This represents a red-shift of ca. 40 nm compared
to 130. The FF value of 0.88 is similar to that of 130 (FF = 0.87).
When four electron-donating OMe substituents are introduced
to form 146, there is a further ca. 40 nm red shift of the main
absorption band maximum,275 while the introduction of
ethylthiophene groups results in a bathochromic shift of
Fig. 17 The absorption spectra of 143 (1) and 144 (2) and their corre- 54 nm. 146 and 147 emit at exceptionally long wavelengths
sponding meso-substituted porphyrins (6 and 9) in toluene. (Reprinted
beyond 700 nm. The thiophene moiety plays a key role in
with permission from ref. 274. Copyright r 2011 Wiley-VCH Verlag GmbH &
Co. KGaA, Weinheim.) extending the p-conjugation system. The FF value decreases
in the same order as the red-shifts of the spectral band, from
0.88 to 0.49, to only 0.20, due in part to an increase in ISC
porphyrin ring is an effective method for obtaining a bath- caused by the heavy atom effect of the sulfur atoms.275,276
ochromic shift of the main absorption band, a major drawback The main absorption and emission bands of the benzo-
in the context of 143 and 144 is that the dyes do not fluoresce. fused and styryl-substituted 148 dye are shifted into the NIR
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region.139 The incorporation of a –NMe2 group onto the styryl form 158, there is a marked decrease in the quantum yield to
group provides a sensor for pH. Interestingly, 148 displays low only 0.08.
fluorescence anisotropy. Many NIR dyes with long polymethine Further red-shifts of this class of BODIPY dye can be
chains, such as styryl dyes, have rather high anisotropies. Low achieved by grafting styryl groups onto the BODIPY core to
anisotropies can be useful when molecules are used as markers form dyes 159–161.280 These structures demonstrate that a
for biological superstructures, since the anisotropy can be meso-methyl group can not only undergo a Knoevenagel reac-
modified considerably upon incorporation of the marker into tion, but can compete with the 3,5-position methyl groups in
the restricted environment of a biomolecule.139 A series of this regard. BODIPY 159 is green in color under ambient
asymmetric benzo-fused BODIPYs with alkynyl groups at the conditions (lmax = 680 nm) and exhibits strong fluorescence
a-positions, 149–152, were recently prepared to provide linkers emission in the NIR region (lem = 705 nm) with a quantum
to other aromatic groups.277 The introduction of the alkynyl yield of 0.75 in CH2Cl2. There are significant red-shifts of the
group was achieved with a Sonogashira coupling reaction. In absorption and emission bands of 71 and 74 nm, respectively,
CH2Cl2, these dyes exhibit typical BODIPY absorption and relative to the spectra of 157. In contrast, the meso-substituted
emission properties, with bands centered at 612–618 and 160 dye absorbs at 608 nm and emits at 687 nm, and has the
625–633 nm, respectively. No significant solvatochromic shifts largest Stokes shift (1891 cm1) reported for this series of dyes.
are observed. Although high FF values between 0.6–0.9 have The absorption and emission bands of 161 and 159 have been
been reported for 147, 150 and 152, a lower value of FF = 0.44 reported to lie at similar wavelengths. This demonstrates that
has been reported for 151. This can be attributed to the the meso-styryl substituent does not have a significant effect on
presence of a low-lying charge separated S1 state, since there the p-conjugation system of the BODIPY core. There is a 491
is an electron-rich 2-ethynylthiophene moiety and the BODIPY torsion angle between the plane of the BODIPY core and that
core is electron deficient. of the meso-styryl ring. In a similar manner to 92–95,245 the
When an anisole substituent is added to form 153, the main meso-styryl-substituted 160 dye fluoresces only weakly with a
absorption band lies at 617 nm in THF, which represents a quantum yield of less than 0.01.
blue-shift of 17 nm relative to that of 145. This is related to the
lack of co-planarity between the two p-systems due to the steric 5.8 Aza-BODIPYs
hindrance caused by the o-methoxy groups on the phenyl One of the most significant strategies for shifting the spectral
substituents. In the crystal structure of 153, the average dihedral bands of the BODIPY to the red is the incorporation of a
angles between the plane of the o-methoxyphenyl group and the nitrogen atom at the meso-position to form an aza-BODIPY
indacene plane is 85.71, which is much larger than the 571 angle in dye. This strategy can be readily combined with other structural
the structure of 145. The FF value of 0.91 is similar to that of modifications involving the substitution or fused-ring-expansion of
145.258 Demethylation of 153 with BBr3 and simultaneous cycliza- the pyrrole moieties. The properties of tetra-aryl, conformationally
tion to form a spirobi[1,3,2]oxazaborine moiety affords a structu- restricted, and b-aromatic-fused and a-substituted aza-BODIPY
rally constrained dye 154 in high yield.258 The absorption and structures will be examined in depth.
emission bands lie at 711 and 733 nm, respectively, and are red 5.8.1 Tetra-aryl systems. In aza-BODIPY dyes such as
shifted by 94 and 81 nm relative to the spectra of 153. The FF value 162,188 the meso-carbon is replaced by an aza-nitrogen atom.
decreases to 0.58. Further modifications of the substituents on the There is a bathochromic shift of approximately 80 nm com-
b-fused benzo ring lead to significant bathochromic shifts of the pared to the analogous tetrasubstituted BODIPY analogue 35
main spectral bands. As a result, the absorption bands of 155 and (Fig. 6), since there is a marked stabilization of the LUMO due
156 are red shifted from 711 nm to 748 and 733 nm, respectively, to a large MO coefficient at the meso-position where the
in THF. No FF values have been reported. Surprisingly, when films electronegative nitrogen atom is introduced. The introduction
are prepared on a glass plate, the film for 155 exhibits an intense of electron-donating –OMe and –NMe2 para-substituents onto
absorption band that stretches out to 1060 nm with a maximum of the phenyl substituents at the 3,5-positions to form 163 and 164
922 nm, due to aggregation effects. It should be noted that 156 can results in additional red-shifts of the absorption maximum
be used as a photosensitizer in polymeric solar cells, since the from 650 nm to 688 and 799 nm, respectively.188,281 There is
incorporation of the 3-hexylthiophene-substituent improves the a destabilization of both the LUMOs and the HOMOs of 163
photovoltaic performance.278,279 and 164 due to the inductive effects associated with the para-
Recently, dyes 157 and 158 have been reported which have substituents. The large MO coefficients at the 3,5-positions
pyrrole and indole substituents at the 3-position and a benzene result in a relative destabilization of the HOMO due to the
ring fused at the b-positions of the same pyrrole moiety.280 The mesomeric interaction between the aryl substituents and the
absorption (lmax = 609 nm) and emission (lem = 631 nm) bands BODIPY chromophore. The incorporation of electron-donating
of 157 exhibit significant red-shifts of 106 and 110 nm, relative substituents at the para-positions of 1,7-position phenyl sub-
to those of 20, and it has a high FF value of 0.61 in CH2Cl2. As stituents results in a smaller red-shift effect relative to the
the number of alkyl substituents on the other pyrrole moiety is corresponding 3,5-position analogues, since there are smaller
increased, the absorption and emission bands are steadily MO coefficients at these positions in the HOMO (Fig. 3).
shifted to longer wavelengths. When an additional fused benzo For example, the absorption bands of 165189 and 166,282 the
group is added at the a-positions of the other pyrrole moiety to 1,7-substituted analogues of 163 and 164, lie at 664 and 763 nm,
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a blue-shift of 24 and 36 nm, respectively. The absorption and Thiophene-substitution at the 2,6-positions to form 171 results
fluorescence spectra of the amino-substituted structures of 164 and in a broadened and hypsochromic absorption band at 650 nm
166 exhibit a strong pH-dependence across a broad pH range. with a relatively low emax value. This value is the same as for 162
When 2-pyridyl substituents are incorporated at the 1,7-positions and indicates that the thiophene moieties at the 2,6-positions do
to form 167 a well-defined coordination pocket is formed which can not have any influence on the wavelengths of the main absorp-
be used to carry out a ratiometric sensing of Hg2+ in the NIR tion bands of 171. DFT geometry optimizations predict a
region.283 The absorption band maximum can be red-shifted by propeller-like structure of the peripheral (het)aryl-rings in 171
92 nm into the red region by replacing the phenyl rings at the 1,3,5,7- with dihedral angles of between 561 and 601. In contrast, the
positions of 162 with thiophenes to form 170. There are two possible thiophene moieties of compounds 168–170 have smaller dihedral
explanations for this. Firstly, the introduction of electron-rich thio- angles of between 141 and 191, while the phenyl rings of 168 and
phenes has a similar effect to that of an electron-donating sub- 169 result in angles of between 281 and 361. This confirms the
stituent leading to a relative destabilization of the HOMO due diminished influence of thiophene substituents when they are
primarily to the larger MO coefficients at the 3,5-positions introduced at the 2,6-positions due to steric hindrance.284
(Fig. 3). Secondly, there are smaller torsion angles between the 5.8.2 Conformationally restricted systems. Conformation-
thienyl rings and the BODIPY core than is the case with phenyl ally restricted aza-BODIPY dyes have markedly red-shifted
rings.284,285 A greater red-shift is observed for the 3,5-thiophene absorption bands with high molar extinction coefficients.
substituted aza-BODIPY structure of 168 (68 nm) relative to 162, When the free rotation of aryl substituents is restricted at both
than for the 1,7-thiophene substituted structure of 169 (33 nm). the 3- and 5-positions by forming 173 a very high e value of
The molar extinction coefficients observed for 168–170 differ 159 000 mol1 cm1 is obtained for the main absorption band.
markedly based on the substitution pattern (120 500 mol1 cm1 The band lies at 740 nm, a red-shift of 52 nm, relative to the
for 168, 110 000 mol1 cm1 for 169, and 78 000 mol1 cm1 for spectrum of 163. Since 173 possesses a moderately high FF
170). The absorption and emission spectra of these compounds value in the NIR region, it is potentially suitable for a wide range of
are not sensitive to solvent polarity, which suggests that applications. In the structure of 172, only one side is restricted. The
they could be used in biotechnology applications.284,285 spectral bands lie at shorter wavelengths than those of 173 and it
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has a much lower molar extinction coefficient, since the phenyl value. This is consistent with the trends observed for the BODIPYs
ring is no longer forced into a co-planar conformation with the in the previous section, since the oxidation of a carbocyclic
BODIPY core. The heterocyclic restricted structure of 174 results in restricted ring system increases the conformational flexibility of
a lower fluorescence quantum yield due to ISC to the triplet the molecule.286,287
manifold resulting from the heavy atom effect associated with The structure of 178 contains B–O bonds which link the
the sulfur atoms. The non-symmetric structure of 175 results in a central boron atom to the ortho-positions of phenyl rings
slightly higher FF value relative to 173. The absorption band lies at substituted at the 3,5-positions.289 The absorption and
a shorter wavelength because of the absence of one of the electron emission maxima are red shifted by 88 and 58 nm and there
donating methoxy substituents. BODIPY 176 also has a lower FF is a 7-fold increase in the quantum yield relative to the
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unconstrained structure of 177.288 A further red-shift of 37 nm hexane and acetonitrile, respectively, and there is a significant
is observed upon the introduction of electron-donating meth- red-shift of the main spectral bands. The fluorescence
oxy substituents to form 179. The significant red-shift observed quenching in polar solvents can be attributed to the formation
in the spectral bands of the conformationally restricted mole- of a low-lying charge-separated S1 state resulting in efficient
cules can be ascribed to the enhanced coplanarity between nonradiative relaxation through conical intersections formed
the p-systems of the BODIPY core and the aryl groups at the between the potential-energy surfaces of the ground and
3,5-positions.289 excited states. BODIPY 182 can be used as a ratiometric ‘turn-
5.8.3 b-Aromatic-fused and a-substituted aza-BODIPYs. on’ NIR fluorescent sensor for changes in pH.186 The incorpora-
There is a marked red-shift of the absorption and emission tion of 1,2-naphtho-fused rings to form 184 results in a 25 nm
bands of benzo-fused aza-BODIPYs 180–183 relative to the red-shift of the absorption band relative to that of 180, along
spectra of the analogous 1,3,5,7-tetraaryl aza-BODIPYs. For with a small change in the other spectroscopic properties.186
example, fused-ring-expansion with benzene rings to form The pyrazine-fused aza-BODIPY 185 has an intense absorption
180 results in a 62 nm red-shift of the absorption band band at 685 nm, which lies 24 nm to the blue of that of 180. The
compared to that of 162.196,197 In DFT calculations (Fig. 6), blue-shift is probably due to the higher electronegativity of the
there is a slight narrowing of the HOMO–LUMO gap of 180 pyrazine nitrogen atoms, which causes an increase in the
relative to that of 162. The destabilization of the HOMO is HOMO–LUMO band gap (Fig. 18). 185 may find applications
greater than that of the LUMO because there are relatively large as a colorimetric and fluorometric sensor for the NH4+ ion.290
MO coefficients on the benzo fragment.
In a similar manner to that described earlier for 21 and 30, 5.9 Bis-BODIPYs
31 and 32, 52 and 61, 105 and 106, and 162, 168 and 170, Red shifts of the absorption bands can also be obtained by
substitution with thiophene rings to form 183, or the incor- forming BODIPY dimers. The properties of directly linked
poration of electron-donating groups at the para-position of dimers and coplanar fused dimers will be examined in depth.
phenyl rings at the 3,5-positions to form 182, results in a 5.9.1 Directly linked bis-BODIPYs. Slight red-shifts of the
marked red-shift of the main spectral bands to longer wave- main spectral band wavelengths are usually observed for
lengths, with significant emission intensity observed in the NIR directly linked bis-BODIPYs 186–190 relative to the corre-
region.198 There is a large relative destabilization of the HOMO sponding monomers. For example, there is almost no red shift
of 183 (Fig. 6), due to a strong mesomeric interaction between of the absorption maxima of the meso–meso and meso-b linked
the thiophene substituents and the core BODIPY chromophore. dyes 186 and 187 relative to the corresponding tetramethyl-
Although smaller extinction coefficients have been reported BODIPY, but a large Stokes shift is observed for the meso–meso
when electron-withdrawing fluorine atoms are added at the linked dye 186. 186 and 187 are potentially useful for photo-
para-positions to form 181, the absorption and emission band dynamic therapy applications due to the interactions between
maxima and the FF value remain almost unchanged.196 When the two BODIPY chromophores in the excited state.291–293 The
dimethylamino substituents are introduced at the para- absorption spectrum of the a–a linked dye 188 is characterized
position of the phenyl rings of 182, the FF value exhibits a by two major bands at 489 and 562 nm, which is consistent
marked solvent dependence with values of 0.10 and 0.01 in with an exciton splitting effect. The fluorescence emission
spectrum of 188 contains a broad emission band at 650 nm
with a Stokes shift of 88 nm with respect to the lowest-energy
absorption band.294–296 The b–b linked BODIPY 189 has a
typical cyanine-type absorption spectrum. Although there is
an increase in the width of the main spectral band relative to
the corresponding monomer, the molar extinction coefficient of
ca. 150 000 M is three times greater than that of the monomer.297–300
The absorption and emission profiles of the 1,10 -linked dimer 190
resemble those of the monomer with a set of vibronic bands at
higher and lower energies. This demonstrates that there is minimal
ground-state interaction or excitonic coupling between the two
chromophores. The fluorescence quantum yield of 190 is signifi-
cantly lower, however, and exhibits a strong dependence on solvent
polarity with FF values ranging from 0.67 in toluene to 0.05 in
dichloromethane and 0.00 in DMSO. This is consistent with the
formation of a nonemissive S1 state with strong charge-transfer
character. The possibility that dimer 190 can undergo symmetry-
breaking internal charge transfer has been confirmed by cyclic
Fig. 18 Energy-level diagram for the frontier p-MOs of 180 and 185. The
nodal patterns of each MO are shown at an isosurface value of 0.02 a.u.
voltammetry.121
(Reprinted with permission from ref. 290. Copyright r 2011 Royal Society 5.9.2 Aromatic-fused bis-BODIPYs and analogues. Typi-
of Chemistry.) cally, p-fused bis-BODIPYs exhibit narrow and intense
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absorption and emission bands in the red/NIR region with in the same order from 661 nm for 193 to 692 nm for 195
high molar absorption coefficients (4100 000 M1 cm1) and (Fig. 19). The absorption maximum of the C2v symmetry
moderate FF values (40.3). This makes these dyes promising benzene-fused bis-BODIPY syn-196 lies at 692 nm, while the
candidates for applications in the NIR region. Bis-BODIPY 191 absorption maximum of the C2h symmetry anti-197 isomer lies
contains a pyrrolopyrrole (PPCy) moiety and provides a good at 758 nm. These bis-BODIPYs emit strongly at 703 and
example of the effects of forming a more rigid chromophore. 774 nm, respectively.308 When benzoBODIPY chromophores
There is a narrowing of the vibronic bands (Dn E 500 cm1) are fused with a shared bridging benzene, the absorption and
and an increase in the e00 values, since there is a shift of the emission maxima of the C2v and C2h symmetry isomers 198
Franck–Condon factors in favor of the main electronic transi- and 199 lie in the NIR region. The absorption and emission
tion. The large bathochromic shift observed on moving from bands of 199 at 848 nm and 868 nm are more highly red-
191 to 192 is probably related to the differing s-inductive shifted than those of 198 at 775 nm and 781 nm. However, the
effects of the BF2 and BPh2 moieties. The emax value of 192, benzene-fused bis-benzoBODIPYs are labile under aerobic
the BPh2 complex, is higher, since there is a decrease in the conditions and readily decompose when dissolved in
width of the main spectral bands and an increase in the solution.308 The difference between the syn and anti isomers
strength of the main electronic 0–0 band. Although the FF can be explained using the results of TD-DFT calculations.308
value decreases slightly as the polarity of the solvent increases, The energies of the HOMOs are similar, but the LUMO energy
it remains remarkably high in DMSO. PPCy derivatives are of the anti isomer is lower than that of the syn isomer, leading
likely to form excellent NIR fluorophores in aqueous environ- to a much smaller HOMO–LUMO gap (Fig. 20). The extra
ments, therefore, once appropriate substituents are intro- stabilization of the LUMO of the anti isomer results from
duced.301,302 PPCy dyes can be synthesized through the the delocalization of the LUMO through the benzo bridge,
condensation reaction of diketopyrrolopyrrole with different since there are significant MO coefficients on the middle set
aromatic acetonitrile groups. They have potentially useful of carbons of the benzo bridge. In contrast, there is a nodal
spectroscopic properties such as very intense and narrow plane through these atoms in the context of the syn isomer,
absorption bands and strong emission in the NIR region (with which means there is no interaction between the two BODIPY
absorption bands ranging from 684 to 864 nm), high photo- moieties.308
stability, and low chemical reactivity.301–306
Pyrrolopyrrole bis-aza-BODIPYs 193–195 have high FF values 5.10 BODIPY analogues
(40.8) and intense absorption bands with maxima ranging in Although BODIPY dyes are potentially useful in a wide variety of
descending energy from that of 193 (638 nm) to 194 (655 nm) different applications, the solid-state emission properties of
and then to 195 (671 nm) due to changes in the fused-ring most BODIPY derivatives have been found to be relatively poor
moieties.307 The fluorescence emission spectra are red-shifted with low FF values being reported. Recently, borate complexes
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Fig. 19 UV-visible absorption (left) and fluorescence (right) spectra of 193

(light blue), 194 (green), and 195 (blue) in CHCl3. (Reprinted with permis-
sion from ref. 307. Copyright r 2013 Royal Society of Chemistry.)
Fig. 21 The HOMO and LUMOs of 200 and 201. The electron density in
the LUMOs is mainly distributed over part A. For 200, the electron density
in the HOMO is localized on part B. More effective ICT character is
anticipated in the excited state of 200 on this basis, which is consistent
with the results of the spectral studies. (Reprinted with permission from
ref. 331. Copyright r 2008 American Chemical Society.)
in acetonitrile to 564 nm in methanol.331 In contrast with 200,

the emission maxima of 201 differ only slightly as the solvent
polarity is increased and exhibit smaller Stokes shifts. DFT
calculations have confirmed that there is less charge transfer
character between the electron-donating phenalene moiety and
the main p-conjugation system in the S1 state of 201 (Fig. 21).
Both dyes exhibit strong fluorescence with a narrow emission
band and a large Stokes shift, due to weak p–p packing
interactions in the solid-state.331 The absorption maxima of
202 and 203 lie at 616 and 650 nm, respectively, and the main
emission band is red-shifted by 45 nm on moving from 202 to
203.332 The red-shift can be attributed to the expansion of the
p-conjugation system due to the coordination of an additional
Fig. 20 The calculated frontier p-MOs of syn-196 (left) and anti-197
boron atom. The dyes have strong electron withdrawing
(right). (Reprinted with permission from ref. 308. Copyright r 2012 Royal
Society of Chemistry.) properties and are promising candidates for use as n-type
organic semiconductors. The emission band of BODIPY
analogue 204 lies at 642 nm. There is a relatively low FF value
with N–B–O, N–B–N and N–B–C coordinate patterns have due to the strong charge transfer character associated with the
been developed by using the boron atom as a structuring S0 - S1 transition. There are large solvatochromic shifts due to
template for forming rigid and near-planar cyanine struc- the push–pull structure.333
tures.309–330,376,377 Although these compounds usually display 5.10.2 N–B–N analogues. Broad absorption and
large Stokes shifts and significant solid-state emission, only a fluorescence bands are observed in the spectra of 205 with
few of these molecular systems have absorption and emission large Stokes shifts observed both in solution and in the solid
bands in the red/NIR region. In this section, a typical set of state. There is a low-lying LUMO, which makes this compound
these BODIPY analogues have been selected to explore the suitable for use as electron-transport materials in
strategies that can be used to shift the absorption and emission electroluminescent devices.334 Broad envelopes of intense
bands to longer wavelengths. Low symmetry BODIPY analogues bands are observed in the UV regions of the absorption
provide a way to make the potential energy surfaces of the spectra of boron-pyridyl-imino-isoindoline BODIPY analogues
ground and excited states more distinct energetically, leading 206–209 (Fig. 22).335 The spectra are, therefore, more similar to
to large Stokes shifts relative to BODIPY dyes. The growing those of pyrene derivatives than to those of BODIPY dyes. In
diversity of such analogues is sure to further enrich BODIPY CH2Cl2, 206 has a major absorption peak at 361 nm with a
chemistry in the years ahead. shoulder at 379 nm and displays a blue shift of 34 nm
5.10.1 N–B–O analogues. Large Stokes shifts are observed compared to that of boron-pyridyl-isoindoline analogues 205.
for N–B–O dye 200 and the emission spectra are strongly DFT calculations predict an increase of the HOMO–LUMO gap
solvent dependent. The emission maxima vary from 620 nm of 206 relative to 205 due to a stabilization of the HOMO. This
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Fig. 22 The absorption and emission spectra of 206–209 in CH2Cl2. (Reprinted with permission from ref. 335. Copyright r 2014 Royal Society of
Chemistry.)
can be readily explained based on the large MO coefficient on yields of 0.22, 0.09, 0.10, and 0.12 for 206–209, respectively.
the aza-nitrogen and the presence of a nodal plane at this This suggests that the asymmetrical structures significantly
position in the HOMO (Fig. 23). Fused-ring-expansion with enhance the solid-state emission properties.335
benzene rings on the pyridyl (207) and indoline (208) 210, a phenanthro[9,10-d]imidazole-quinoline substituted
moieties results in 26 and 35 nm red shifts of the main dye, has a large Stokes shift of 109 nm in CH2Cl2 and red
absorption bands relative to that of 206. Upon further fused- fluorescence is observed in the solid state.336 The optical
ring-expansion to form 209, which has fused benzene rings on properties for dye 211 are affected only slightly by the solvent
both the pyridyl and indoline moieties, there is a 58 nm red polarity and there is a relatively small Stokes shifts. This is
shift to 419 nm. The extinction coefficient increases from consistent with the presence of a conventional S0–S1 transition
24 400 M1 cm1 for 206 to a maximum of 47 500 M1 cm1 with no significant charge transfer character.337 In contrast,
for 209, due to the extension of the p-conjugation system. 206– large Stokes shifts of over 110 nm are observed for 212 and 213
209 display strong emission with fluorescence quantum yields due to aggregation-induced emission.338,339 212 and its deriva-
of 0.33 (206), 0.74 (207), 0.86 (208) and 0.90 (209). Importantly, tives exhibit exceptional photostability and are competitively
intense solid-state fluorescence is observed, with quantum membrane-specific.338 Dye 214 is synthesized by coordinating
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boron to the green fluorescent protein (GFP) and is usually 216 exhibit weak emission in the NIR region. No FF values have
referred to as GFP–chromophore. The compounds are neutral, been reported.341
uncharged, and highly fluorescent and can be readily sulfo-
nated and modified to include a point of attachment for
biomolecules.340 The mono-BF2 compound 215 has an intense 6. Conclusions and perspectives
absorption band at 649 nm. The incorporation of a second BF2
moiety to form 216 results in a further red-shift of the absorp- Various structural modification strategies (Fig. 24) can be used
tion maximum to 743 nm. 216 is unstable and gradually to shift the wavelengths of the main BODIPY bands into the
decomposes to the mono-BF2 structure of 215. Both 215 and red/NIR region. When tetramethyl-BODIPY 51 is used as a
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reference point for the parent dipyrrin chromophore, the

following trends are observed:
Aryl substitution: a red shift of ca. 55 nm for phenyl
groups at the 3,5-positions (21) and 38 nm at 1,7-positions (33).
Ethynylphenyl substitution: a red shift of ca. 114 nm for
ethynylphenyl groups at the 3,5-positions (46) and 70 nm at the
1,7-positions (41).
Styryl substitution: a red shift of 129 nm for styryl sub-
stituents at the 3,5-positions (62) and 72 nm for substitution at
the 1,7-positions (66), there is a further red-shift of 44 nm when

there are styryl substituents at 1,3,5,7-positions (77 to 79).
Heteroatoms: the presence of heteroatoms at the 3,5-
positions such as Se (99) or Te (100) results in red-shifts of 86
Fig. 23 The energy level diagram from left to right for the frontier and 120 nm, respectively.
p-MOs of a boron-pyridyl-imino-pyrrole model compound and 206– aza-BODIPYs with aryl substituents: a red shift of ca. 80 nm
209 using the B3LYP functional with the 6-31G(d) basis set. The angular
when the meso-carbon is replaced by a nitrogen atom (35 to 162,
nodal patterns are shown at an isosurface value of 0.02 a.u. (Reprinted
with permission from ref. 335. Copyright r 2014 Royal Society of 145 to 180).
Chemistry.) Aromatic ring fusion: phenyl ring fusion at the b-position
(130) leads to a red-shift of 97 nm, this strategy enables the
Fig. 24 Selected structurally-modified BODIPYs that absorb at different wavelength ranges from 500 to 850 nm.
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extension of the p-conjugation system of the indacene plane along The versatility of the structural modifications that can be
with the attachment of functional groups at the 3,5-positions, such made to the BODIPY core has led to the preparation of a wide
as styryls or ethnylphenyl. This strategy has the potential to yield range of BODIPYs, with spectral bands in the 650–850 nm
intense NIR region chromophores while maintaining the ability to ‘biological window’. Despite the considerable progress that has
incorporate all of the other functionalization possibilities. been made in the synthesis of NIR region BODIPY derivatives,
Phenanthro-fused BODIPYs (134) absorb and emit in the red region theoretical calculations have not been utilized to the extent they
with intense and narrow emission bands (FF = 1.0 is sometimes could have been during the analysis of the structure–property
achieved) while retaining the possibility of further modification relationships.41,71,342–345 For example, very few calculations
at the 3,5-positions. Taking into account the trends observed for have been carried out to address why substituents have mark-
3,5-dimethylaminostyryl substituents, it appears that it may be edly differing effects depending on the substitution position,
possible to synthesize BODIPY dyes that absorb beyond 850 nm. despite the likelihood that an MO theory approach would
Rigidization: a red-shift of 52–94 nm upon rigidization of provide new insights in this regard. The considerable progress
two 3,5-diphenyl groups (21 to 102, 123 to 124, 127 to 128, 153 that has been made in this regard in porphyrinoid chemistry in
to 154, 163 to 173, 177 to 178), which can be viewed as involving recent years suggests that this approach would greatly facilitate
the fusion of two dihydronaphthalene groups to the BODIPY the rational design of red/NIR absorbing BODIPY dyes
core. This leads to an increase in the FF value. Rigidization of for applications.346–350 This review has attempted to address
two 3,5-distyryl groups with oxygen and sulfur atom bridge this issue.
linkers (62 to 115, 71 to 122) results in red-shifts of 23 and To effectively use NIR region BODIPY dyes for labeling
27 nm, respectively, and leads to other beneficial spectroscopic during biological analyses, or as biomarkers in biomedical
properties such as high extinction coefficients and FF values. applications such as imaging diagnosis, a hydrophilic character
Electron-donating para-position substituents: a red-shift of is usually required. The range of synthetic methodologies
28–41 and 70–127 nm after the introduction of electron donating that are available for the preparation of water-soluble dyes is
methoxy and dimethylamino groups, at the para-positions, of the limited, however. This represents a bottleneck that impedes
3,5-diphenyl rings (39 to 40, 62 to 63, 162 to 163 to 164). further progress in biomedical analysis. To date, although a few
Combinations of the above: for example, the incorporation water-soluble BODIPY derivatives have been prepared by intro-
of a dimethylamino group at the para-positions of the 3,5-diaryl ducing oligo-(ethyleneglycol) chains,351–355 nucleotides,356 sul-
rings of a benzo-fused aza-BODIPY 182 results in a markedly fonated peptides,357–359 carboxylates,360–367 sulfonates,363–370
red-shifted absorption band, which lies at 794 nm. phosphonate371 or betaine moieties,372 there has been only
Positions where substituents are introduced: modification limited progress where the preparation of p-extended dyes
at the 3,5-positions results in greater red-shifts of the absorption emitting in the 650–850 nm window is concerned. In most cases,
and emission maxima than those observed when substituents solubility is achieved by linking a polar group such as a
are introduced at the 2,6- and 1,7-positions. The Stokes shifts negatively charged sulfonate to the dye. The negative charge is
observed for BODIPYs with substituents at the 2,6-positions are potentially problematic, however, since it may hinder the binding
usually larger than those for dyes with substituents at the 1,7- or of negatively charged bioanalytes.31,373
3,5-positions, since there is more flexibility in the molecular In addition to the hydrophobicity problem, aggregation in
geometry upon photoexcitation. aqueous solution is another major drawback in the case of NIR
Five-membered heterocyclic substituents: thiophenes and region BODIPY dyes, since it results in quenching of the
pyrroles play a similar role to electron-donating phenyl sub- fluorescence intensity. Recently, Ziessel and co-workers
stituents in causing a red shift of ca. 80 nm (21 to 30, 31 to 32, reported a promising structural modification strategy in this
162 to 168 to 170, 180 to 183). These results can be ascribed to regard.374 A bulky polar substituent can be introduced at the
the smaller torsion angles and their stronger electron donating boron center, in a manner that hinders aggregation in aqueous
properties. media, thereby leading to bright fluorophores with moderate
Other strategies, which have also proven to have a beneficial fluorescence quantum yields. Although there is a significant
effect on the spectroscopic properties, can be summarized as follows: demand in biotechnology fields for water-soluble NIR region
Inhibiting the rotation of meso-substituents increases the dyes, suitable NIR emitting BODIPYs that could meet this
FF value. For example, methyl substituents at the 1,7-positions demand are yet to emerge.
result in an increase in the FF value from 0.38 (102) to 0.72 For most NIR region BODIPY dyes, the absorption and
(103). The increase of the FF value from 0.41 (124) to 0.72 (126) emission bands overlap significantly, leading to an interaction
when the ortho-position protons of meso-aryl substituents are between the excitation beam and the emission signal. Fluores-
replaced with methyl groups provides another good example. cence resonance energy transfer cassettes, which can separate
Although modifications at the meso-position often have the emission and excitation bands more effectively, could prove
only a minor influence on the absorption and emission useful for applications, especially water-soluble multiplex cas-
maxima, the incorporation of a strongly electron-withdrawing settes.22 Alternatively, upconversion luminescence is a process
meso-CF3-substituent group results in a bathochromic shift of wherein NIR light is converted to higher energy light through
ca. 40 nm in the spectral bands relative to meso-aryl-BODIPYs the sequential absorption of multiple photons or energy trans-
(21 to 31, 30 to 32, 116 to 117). fer. The design of new NIR region BODIPY dyes, with spectra
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which are compatible with rare-earth upconversion nanophos- 3 E. Terpetschnig and O. S. Wolfbeis, in Near-Infrared Dyes
phors, or with sensitized triplet–triplet annihilation, is yet to be for High Technology Applications, ed. S. DIhne, U. Resch-
explored.13,375 Future research on NIR region BODIPY dyes is Genger and O. S. Wolfbeis, Kluwer Academic, Dordrecht,
likely to revolve around applications in biotechnology such as 1998, pp. 161–182.
genomics and diagnostics. Nanotechnology can provide a wide 4 L. Yuan, W. Lin, K. Zheng, L. He and W. Huang, Chem. Soc.
range of different platforms for the formation of conjugates Rev., 2013, 42, 622–661.
and this could provide a viable platform for the delivery of 5 T. Vo-Dinh, Biomedical Photonics Handbook, Taylor & Francis,
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6 S. A. Hilderbrand and R. Weissleder, Curr. Opin. Chem.
Biol., 2010, 14, 71–78.

Abbreviations 7 J. V. Frangioni, Curr. Opin. Chem. Biol., 2003, 7,
BODIPY Difluoroboron dipyrromethene or 4,4-difluoro- 626–634.
4-bora-3a,4a-diaza-s-indacene 8 Z. Cheng, Z. Wu, Z. Xiong, S. S. Gambhir and X. Chen,
DDQ 2,3-Dichloro-5,6-dicyano-p-benzoquinone Bioconjugate Chem., 2005, 16, 1433–1441.
MO Molecular orbital 9 R. Weissleder, Nat. Biotechnol., 2001, 19, 316–317.
HOMO Highest occupied molecular orbital 10 V. Ntziachristos, J. Ripoll, L. H. V. Wang and R. Weissleder,
LUMO Lowest unoccupied molecular orbital Nat. Biotechnol., 2005, 23, 313–320.
DFT Density functional theory 11 A. Becker, C. Hessenius, K. Licha, B. Ebert, U. Sukowski,
TD-DFT Time-dependent density functional theory W. Semmler, B. Wiedenmann and C. Grotzinger, Nat.
NIR Near-infrared Biotechnol., 2001, 19, 327–331.
PET Photoinduced electron transfer 12 C. L. Amiot, S. Xu, S. Liang, L. Pan, J. Xiao and J. Zhao,
ICT Intramolecular charge transfer Sensors, 2008, 8, 3082–3105.
CT Charge transfer 13 J. Zhou, Z. Liu and F. Li, Chem. Soc. Rev., 2012, 41,
THF Tetrahydrofuran 1323–1349.
MTHF Methyltetrahydrofuran 14 W. Wu, L. Yao, T. Yang, R. Yin, F. Li and Y. Yu, J. Am. Chem.
EtOH Ethanol Soc., 2011, 133, 15810–15813.
MeOH Methanol 15 J. O. Escobedo, O. Rusin, S. Lim and R. M. Strongin, Curr.
MeCN Acetonitrile Opin. Chem. Biol., 2010, 14, 64–70.
DMSO Dimethyl sulfoxide 16 Reviews in Fluorescence 2009, ed. C. D. Geddes, Springer
PBS Buffer phosphate-buffered saline pH 7.4 Science + Business Media, LLC, 2011, 10.1007/978-1-4419-
GFP Green fluorescent protein 9672-5_4.
e Molar absorption coefficient 17 M. Fu, Y. Xiao, X. Qian, D. Zhao and Y. Xu, Chem. Com-
F Fluorescence quantum yield mun., 2008, 1780–1782.
labs Wavelength of maximal absorbance 18 Y. Koide, Y. Urano, K. Hanaoka, T. Terai and T. Nagano,
lem Wavelength of maximal fluorescence emission J. Am. Chem. Soc., 2011, 133, 5680–5682.
spectral radiant power 19 Y. Koide, Y. Urano, K. Hanaoka, T. Terai and T. Nagano,
N.A. Not available ACS Chem. Biol., 2011, 6, 600–608.
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23 K. Umezawa, Y. Nakamura, H. Makino, D. Citterio and
This research was supported by NSFC (21371090 & 21101049), K. Suzuki, J. Am. Chem. Soc., 2008, 130, 1550–1551.
the Major State Basic Research Development Program of China 24 N. Tyutyulkov, J. Fabian, A. Mehlhorn, F. Dietz and
(Grant No. 2011CB808704 & 2013CB922101). The theoretical A. Tadjer, Polymethine Dyes, St. Kliment Ohridski University
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Structural modification strategies for the rational

design of red/NIR region BODIPYs†

1. Introduction and optical sensors for biological and medical applications.1–6

Dr Hua Lu received his PhD Dr John Mack obtained a BSc

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often encountered. Rotation and photoisomerization of their

600 nm.3,29,30 Moreover, since they are positively charged ions,

Dr Yongchao Yang received his Prof. Zhen Shen received a PhD

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Fig. 4 Absorption and emission spectra of 1,3,5,7-tetramethyl-meso-

Fig. 3 Nodal patterns of the HOMO and LUMO of an unsubstituted

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Scheme 1 General synthetic methods for red/NIR BODIPY derivatives.

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a tetravinyl configuration.140–142 Knoevenagel condensation

3.2 Aromatic ring fusion

3.2.1 Reactions of aromatic ring-fused pyrroles with aldehydes.

Scheme 4 The condensation reaction of 1,3,5,7-tetramethyl-BODIPY with aromatic aldehydes.

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chalcones and nitromethane, or cyanide, followed by a condensation

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intensity and results in a marked blue-shift in its band maximum. It

5.5 Fused-ring systems

co-planarity between the p-systems of the aryl substituents by

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5.6 Fused-ring-expansion systems

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the a-position, and BODIPY moieties have also be fused with

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solid state.268 The naphthobipyrrole derived BODIPY 136 has

at 681 and 658 nm, respectively.270 When two fluorantho[8,9-f ]-

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This is the norm for Ni(II) porphyrins, however, due to the

5.7 b-Aromatic ring-fused and a-substituted BODIPYs

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