Poly-halogenated aza-bodipy dyes with improved solubility as a versatile synthetic platform for the design of photonic materials

Article abstract of DOI:10.1039/d0nj02631j

The optimization of the solubility in organic solvents of halogenated aza-dipyrromethenes was achieved by substitution of the upper phenyl moieties by branched long alkoxy chains (1f) or by using an OMe-OHex-OMe pattern (1h). These results allowed us to prepare original tetra-halogenated aza-dipyrromethenes that were used as a synthetic platform to access highly functionalized aza-bodipy dyes for various potential applications including PDT, imaging, or nonlinear optics. This journal is

Full text of DOI:10.1039/d0nj02631j

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Poly-halogenated aza-bodipy dyes with improved solubility as
versatile synthetic platform for the design of photonic materials.
Sylvain David,a Guillaume Pilet,b Gérard Berginc,c Chantal Andraud,*a Olivier Maury*ac
Received 00th January 20xx,
Accepted 00th January 20xx
The optimization of the solubility in organic solvents of halogenated aza-dipyrromethenes was achieved by substitutions of
the upper phenyl moities by branched long alkoxy (1f) or by using a OMe-OHex-OMe pattern (1h). These results allowed us
to prepare original tetra-halogenated aza-dipyrromethenes that were used as synthetic platforms to access highly
functionalized aza-bodipy dyes for various potential applications including PDT, imaging, or nonlinear optics.
DOI: 10.1039/x0xx00000x
The main reason for the enthusiasm for this class of dyes lies on their
versatile structure featuring different functionalization positions,
their important chemical and electrochemical stability and their
Introduction
Aza-bodipy dyes whose characteristic architecture is depicted
Figure 1, are a versatile class of chromophore featuring strongly red-
shifted absorption and high extinction coefficient that became very
popular following pioneering works of O’Shea’s group in the early
00’s.1,2 Their particular photophysical properties have been
extensively studied for a wide range of applications: (i) in biology,
either for fluorescence3 and photoacoustic imaging4 or
photothermal5 and photodynamic therapy2a,6 or sensing;7 (ii) in
material sciences for organic electronics and photonics (e.g.
photovoltaics, nonlinear optics (NLO), optical power limitation
(OPL)…).8
intense absorption bands that can be tuned by the substitution and
shifted in the red- or infrared spectral range.9 From a synthetic point
of view, the preparation of these functional chromophores generally
requires a multistep procedure with intermediates featuring reactive
groups like halogens (Br, I) for further cross-coupling reactions.8c,9b,10
However, whereas the aza-bodipy dyes present generally an
acceptable solubility in most of the common organic solvents, their
aza-dipyrromethene precursors, and particularly bis- or tetra-
halogenated intermediates present a really poor solubility leading to
difficult purification steps and product characterization, limited
reactivity, resulting in poor yields in the case of multi-steps synthesis
(Figure 1).11 Solubility improvements are generally intended by
addition of alkyl substituents but rational reports concerning this
aspect are really scarce in the literature12 and completely absent for
aza-bodipy dyes. In this context, we decided to carry out a systematic
solubility improvement study on one di-bromo-aza-dipyrromethene
intermediate (1a) involved in advanced functional dye synthesis. 1a
presents a modest solubility in common organic solvents and its
further halogenation attempts were described as almost impossible
due to the insolubility of the reaction products.11a Introduction of
two m-OMe groups reported by Ramaiah et al. enabled the
preparation of polyhalogenated compounds but the solubility was
still not optimized.13 In this article, we report the synthesis of a series
of analogous of 1a where the phenyl fragments located at the upper
positions (positions 1,7) were further substituted by alkyl groups (e.g.
-ter-butyl (1b)), by linear or branched alkoxides (e.g. hexyloxy (1c),
nonan-5-yloxy (1d), (2-ethylhexyl)oxy, (1e), (2-hexyldecyl)oxy (1f)) or
by three meta and para alkoxides (eg. tris-methoxy (1g), bis-
methoxy, hexyloxy (1h)) as depicted in Figure 2. The maximal
solubility in THF was determined and the most soluble compounds
1f,h were used as synthetic platforms for the preparation of
polyhalogenated derivatives or advanced functional dyes featuring
extended conjugated backbone. In this latter case, the functionalized
Sol
Sol
Sol
Sol
8
N
7
1
N
N
B
X
X
Ar
Ar
6
2
NH
N
N
4
B
N
N
N
3
5
F
F
F
F
X
X
Ar
Ar
Aza-bodipy
core
Functionalized aza-bodipy
Synthetic platform
Figure 1. General structure of aza-bodipy core and poly-halogenated aza-
dipyrromethene intermediate for the access to highly functionalized dyes.
a. Univ. Lyon, ENS Lyon, CNRS, Université Lyon 1, Laboratoire de Chimie, UMR 5182,
46 Allée d’Italie, 69364 Lyon, France. E-mail: olivier.maury@ens-lyon.fr,
chantal.andraud@ens-lyon.fr
b. Univ. Lyon, Laboratoire des Multimatériaux et Interfaces, UMR 5615, CNRS-
Université Claude Bernard Lyon 1, France,
Villeurbanne, France.
6 rue Victor Grignard 69622
c. Thales LAS France, 2 Avenue Gay Lussac, 78990 Élancourt, France.
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
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R1
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R1
R2 R2
DOI: 10.1039/D0NJ02631J
R2
R2
5
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8
O
O
NO2
O
O
N
NH4OAc
R2
NaOH
EtOH
R
H
R2
R2
R1
NH
N
HNEt2
MeOH
EtOH
or
BuOH
R1
Br
Br
R1
Br
R2
R2
9
R2
1
5a-h
4a-h
2a-h
3
10
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Br
Br
C2H5
C4H9
C4H9
C6H13
C8H17
O
O
C6H13
H
C4H9
O
R1 =
R2 = H
O
2a-f
a
b
c
d
e
f
2g
2h
R1 = R2 = OMe
R1 = OC6H13 and R2 = OMe
C4H9
C4H9
C6H13
C6H13
O
O
O
O
C4H9
C4H9
N
N
N
N
NH
N
NH
N
NH
N
NH
N
Br
Br
Br
Br
Br
Br
Br
Br
O
1b
(13%)
1a
(37%)
1c
(39%)
1d
(7%)
C2H5
O
C4H9
O
C8H17
O
C6H13
C6H13
C4H9
C2H5
C8H17
C6H13
O
C6H13
O
O
O
O
O
O
O
O
O
O
O
N
N
NH
N
N
NH
N
N
NH
N
NH
N
Br
Br
Br
Br
Br
Br
Br
Br
1f
(21%)
1h
(8%)
1e
(27%)
1g
(14%)
Figure 2. Reference aza-dipyrromethene 1a and compounds 1b-h studied for solubility improvement. In red are indicated the nature of the solubilizing
substituents. In the upper part of the figure is represented the classical synthetic scheme. Brackets correspond to global yields over 3 steps.
aza-bodipy dyes can be used as pure material for thin film
preparation using spin coating technique or pure material by simple
melting.
depicted in Figures 3 and 4 and crystallographic data, refinement
parameters and selected bonds lengths and angles are compiled in
Tables S1 and S2. It is worth noting that many crystal structures of
aza-bodipy dyes are described in the literature,2,8,9 structures of aza-
dipyrromethene precursors are less common. In both cases, the aza-
dipyrromethene structures are very similar; they adopt the expected
cisoid conformation with a very planar structure and classical bond
distances (Table S2). Due to the larger steric hindrance of 1d
compared to 1g, the crystal packing and molecular arrangement are
different (Figure 4). In the a-direction of the unit-cell, molecules of
1d are organized in a head-to-tail way. Due to the upper site volume,
molecules are offset from each other along the b-axis of the unit-cell.
Then, the crystal packing of these molecules can be viewed as waves
running along the c-axis of the unit-cell stacking on top of each other
along the b-axis of the unit-cell. In case of 1g, volume of the upper
site of the molecule is smaller and molecules stack perfectly on the
top each other along the a-axis of the unit-cell forming planes. Each
plane is separated from its neighbour by co-crystallized THF solvent
molecules.
Results and discussion
Synthetic procedures. The synthesis of the aza-dipyrromethene (1a-
h) was achieved using the classical three steps synthetic procedure
involving (i) the aldol condensation of the desired aldehyde with
4’-bromoacetophenone, (ii) the Michael addition of nitromethane
and (iii) the final cyclisation/condensation step leading to aza-
dipyrromethenes (1a-h) in the presence of ammonium acetate in
refluxing ethanol or butanol.2a All compounds were purified by
1
precipitation or chromatography and characterized by H NMR and
mass spectrometry (see SI for details).
Crystallography. Interestingly, in the case of 1d and 1g, crystals
suitable for X-ray structure determination were obtained by slow
diffusion of dichloromethane in ethanol at RT. Structures are
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diluted solution absorption with a calibration curve previously
3
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7
8
9
saturation concentration (Csat) was determined by comparison of the
established for all compounds (see SI for details, Figure S2). The
experimental protocol was tested several time on 1a to evaluate the
experimental error. The calibration was made twice (Figure S3) and
very similar slopes were found; the error can be estimated to 2%
mainly due to weighing imprecision. Then five different THF
saturated solutions have been prepared leading to an average Csat
(1a) value of 7.6 ± 0.6 mg.mL-1 (Table S3). The uncertainty of the
measure is of about 10%, of course higher than that of the calibration
curve and may be explained by room temperature variation over a
large period of time. This protocol was then applied for all aza-
dipyrromethenes (1b-h) and the results are compiled in the Table 1.
For comparison, we defined the solubility enhancement ratio (RS) as
the ratio of the sample’s saturation concentration to the saturation
concentration of the reference 1a (the values are taken in mmol.L-1).
10
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Figure 3. Crystal structures 1d (left) and 1g (right).
Table 1. Saturation concentration measurements in THF at room
temperature.
a
a
λmax
ε
Csat
Csat
RS b
[nm] [M-1.cm-1] [mmol.L-1] [mg.mL-1]
1a 605
1b 606
1c 618
1d 620
1e 617
41000
-
13
-
19
81
43
8
-
15
72
37
1
c
c
c
c
-
37000
51000
49000
41000
43000
44000
1.5
6.4
3.4
Figure 4. Crystal packing of 1d (left) and 1g (right) along the a-axis and b-axis
of the unit-cell, respectively.
1f
618
101
4
110
3
8.0
1g 614
1h 616
0.3
>124d
>115d
>9.9d
Solubility measurements. The solubility determination was
performed using a method inspired by that of Hill et al. used in the
case of perylene diimide dyes.12 At first, the absorption spectra were
measured (Figure 5) and the extinction coefficients were carefully
determined using a Beer-Lambert Law method (Table 1). All
compounds present rather similar absorption profile with an intense
and broad band around 610 nm. One can notice that introduction of
alkoxy fragment slightly red-shifts the absorption maxima compared
to 1a,b. Then, a saturated THF solution was prepared at room
temperature and filtered off, the filtrate was diluted and the
a : values given with 10% error, b : for a compound X, Rs(X) = Csat(X)/Csat(1a) with the
saturation concentration in mmol.L-1. c: not soluble enough. d: saturation concentration
not reached.
Tetra-halogenated platforms. The high increase in aza-
dipyrromethene intermediates solubility is of great interest for
further functionalization of aza-bodipy dyes. Indeed, with the
modification made on upper 1,7 positions, it is now possible to
halogenate directly side 2,6 positions, to obtain tetra-halogenated
aza-dipyrromethenes. Using most soluble compounds 1f and 1h,
several examples of bromination or iodination of the 2,6 positions
have been prepared in good yields by reaction with bromo-or iodo-
succinimide respectively and are listed in Figure 6. Tetra-halogenated
aza-dipyrromethenes 6-9 present good solubility in common organic
solvents and are the first to be fully characterized by NMR (see SI for
details). These compounds could be used as a synthetic platform for
orthogonal palladium catalyzed cross-coupling reactions or to
prepare corresponding tetra-halogenated aza-bodipy dyes. As an
example, molecule 10 was synthesized by successive iodination and
borylation of intermediate 1f with an 86% yield. This molecule
presents also an excellent solubility and was fully characterized.
Spectroscopic data obtained on molecule 10 are shown Figure 7 and
Table 2. This dye presents a sharp and intense absorption band (λ =
660 nm, ε = 71500 L.mol-1.cm-1) with a slight shouldering around λ =
50000
1a
1c
1d
40000
1e
1f
1g
1h
30000
20000
10000
0
400
500
600
700
Wavelength (nm)
Figure 5. UV-visible absorption spectra of compounds 1a-h in THF.
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560 nm, which is characteristic of aza-bodipy dyes having a strong
cyanine transition character. Fluorescence measurements have been
conducted in DCM and showed a narrow mirror emission band
centered on 723 nm with a negligible quantum yield  < 0.01. This
very weak fluorescence could be explained by the presence of heavy
atoms favoring intersystem crossing and population of the triplet
state via spin-orbit coupling enhancement.11b Singlet oxygen
generation of molecule 10 in DCM was evaluated by measuring
phosphorescence at 1270 nm, using phenalenone as a reference. As
expected, aza-bodipy 10 presents a high singlet oxygen generation
quantum yield Δ = 0.58 which confirms previous observations by
Adarsh et al. on analogous compounds.13 As future perspective, the
tetrahalogenated compounds presented here can have interesting
properties for PDT or photo-acoustic imaging.4,6,13,14
1,0
0,5
0,0
1500
1000
500
0
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Ar
Ar
Ar
Ar
Ar
Ar
N
B
N
N
NXS
BF3.OEt2, DIEA
DCM
X2
X2
X2
X2
400
600
1200
1400
N
N
NH
N
NH
N
CHCl3/AcOH
F
F
 (nm)
X1
X1
X1
X1
X1
X1
Figure 7. Absorption (blue line) and emission (dashed blue line) spectra of
compound 10 in DCM. In red is represented the emission of singlet oxgen
observed after irradiation of 10 (ex = 600 nm).
C6H13
O
C6H13
O
C6H13
O
C6H13
C6H13
O
C6H13
O
O
O
O
O
O
O
O
O
O
O
O
O
O
N
N
N
I
I
Br
Br
I
I
NH
N
NH
N
NH
N
6
7
8
93%
26%
93%
Br
Br
C8H17
I
I
I
I
C8H17
C6H13
C6H13
O
C6H13
C6H13
O
C8H17
C8H17
O
O
R1
R1
R1
R1
R2 R2
R2 R2
R2
R2
R2
R2
C6H13
N
C6H13
N
N
B
N
NH
Pd(PPh3)4, K2CO3
DMF, 100 °C
N
NH
I
I
I
I
NH
N
N
N
N
N
D1-H
F
F
9
10
81%
86%
Br
Br
Br
Br
X
X
1f
; R1 = ODecyl-2-hexyl, R2 = H, X= Br
Figure 6. Synthesis of tetra-halogenated aza-dipyrromethenes and
corresponding aza-bodipy dyes.
1h'
:R1 = 1 = OHexyl, R2 = OMe, X = I
N
N
Hex
Hex
Hex
Hex
11f
11h
: R1 = ODecyl-2-hexyl, R2 = H
: R1 = OHexyl, R2 = OMe
BF3.OEt2, DIPEA
DCM, RT
Advanced photonic dyes. The second application of these improved
solubility aza-bodipy concerned the synthesis of advanced
chromophore for photonics and more precisely the design of
molecular materials for optical power limitation (OPL), i.e. the
protection of optical devices or eyes against incident laser threats.15
In this context, organic dyes featuring optimized nonlinear optical
properties are particularly appealing but required to be used in
extremely high concentration either in solution or as a guest in
materials. In the last decade, our group reported the aza-bodipy dye
N
N
N
R1
R1
B
R2 R2
F
F
R2
R2
N
N
N
12a
B
F
F
N
N
C6H13
C6H13
C6H13
C6H13
12f
12h
(60% over the 2 steps)
(57% over the 2 steps)
N
N
Hex
Hex
12a,
functionalized
at
the
1,7
positions
by
Hex
Hex
dihexylaminophenylethynyl chromophore (Figure 8) which consist in
the benchmark chromophore for optical protection at
telecommunication wavelength (1550 nm) in solution or in sol-gel
material.16 In order to further improve the solubility of this
chromophore in organic solvents, we decided to prepare analogous
dyes, 11f and 11h further functionalized at the top positions (1,7) by
the best solubilizing moieties. The aza-dipyrromethenes 1f and the
Figure 8. Structure of the benchmark dye 12a used for optical limitation at
1500 nm and synthetic scheme for the preparation of 12f,h.
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more reactive analogous 1h’ featuring para-iodo substituents have
been further involved in a Pd-Catalysed Sonogashira cross-coupling.
Classical conditions involving PdCl2(PPh3)2/CuI mainly led to the
formation of the Glaser type homocoupling product. The reaction
was optimized and copper free conditions were found using Pd(Ph3)4
as a catalyst in DMF at 100°C in the presence of potassium carbonate
gave the best yield of formation of the desired product that was
immediately involved in the borylation step without purification. The
global yield after chromatography for this two-steps procedure was
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Figure 10. Solid amorphous powder of compound 12h (left) and glassy
solid obtained after successive heating and cooling (right).
However, the most important modification concerns the
morphological aspect of the dyes: whereas 12a can be isolated as a
microcrystalline powder, 12f is a wax and 12h is an amorphous
powder that becomes a glass after low temperature melting (< 60°C).
As a consequence, these two last molecules formed easily pure
molecular thin films by drop-casting or spin coating from a
concentrated chloroform solution, which was not the case for 12a
(Figure 9). The absorption spectra of these material were measured.
For both molecules, a broadening of absorption spectra was
observed, typical behavior for pure molecular films on a surface,17 as
well as an increase in relative intensity of the higher energy
absorption band around 600 nm compared to the main absorption
peak. Finally, the facility of the processing of these new molecules
will allow the preparation of thick pure molecular films or materials
similar to those prepared by Weder and coworkers18 for several
application including nonlinear optics. Indeed, molecule 12h can be
melted by gentle heating and transfer into a mold. By simply cooling
to RT, 12h forms a glassy solid (Figure 10) which is currently
investigated as material for optical power limiting applications.
1,0
0,8
0,6
0,4
0,2
0,0
400
500
600
700
800
900
1000
 (nm)
Figure 9. Normalized absorption spectra of 12f (blue) and 12h (red) in diluted
dichloromethane solution (full lines) and thin films (dotted lines). In inset is
reported a picture of the pure molecular thins film obtained by spin-coating
of 12h.
57 % and 60% for 12h and 12f respectively and both compounds
were fully characterized (see SI). Importantly these last compounds
present almost identical absorption properties than the benchmark
molecule in dichloromethane solution (Figure 9 and Table 2) with a
minor shift of the main absorption band ( = -4 nm and +5 nm for
12f and 12h, respectively). The emission behaviours of 12f,h are also
very similar to 12a with a luminescence quenching in polar solvent
like dichloromethane and a significant emission above 800 nm in
apolar solvent like toluene (Table 2). One can notice an increase in
emission quantum yield and lifetime in the case of compound 12f.
Conclusions
In this paper, we presented new halogenated aza-dipyrromethenes
and we studied their solubility in common organic solvents, in
particular THF. The substitutions of the upper phenyl moieties by
branched long alkoxy (1f) or by using a OMe-OHex-OMe pattern (1h)
were identified as greatly increasing the solubility compared to the
non-substituted reference molecule 1a by a factor around 10. This
solubility improvement allowed the easy preparation of tetra-
halogenated aza-dipyrromethene which were up to now not fully
described in the literature because of their lack of solubility in
organic solvents. These molecules are useful as synthetic platform to
access highly functionalized aza-bodipy dyes for various potential
application including PDT, imaging, or nonlinear optics. For this latter
application two new dyes bearing the most solubilizing groups have
been prepared by grafting an electron donating group. These
chromophores are analogues to benchmark short-wave infrared OPL
dye but presented very interesting physical properties including low
melting point, high filmability which paves the way for pure
processing opportunities and for the design of thick films or melt
processed materials for OPL.
Table 2. Photophysical properties of aza-bodipy dyes 10, 12a and 12f,h in
dichloromethane at room temperature.
b
a

compound
λmax
ε
λem
τ
[nm] [L. mol-1.cm-1] [nm]
[ns]
-
10
660
740
736
745
71500
57 000
65 000
50 000
723
825a
807a
824a
<0.01
0.04
0.11
0.05
0.58
12a
12f
12h
0.7
1.4
0.7
-
-
-
a : measurment in toluene, (H/OMe)BF2 was used as a reference11 (ϕ = 0.36 dans le
CHCl3). b : phenalenone was used as a reference (ϕΔ = 96 % dans le DCM).
Conflicts of interest
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Thomas, R. Canton-Vitoria, F. D'Souza, N. Tagmatarchis Chem.
There are no conflicts to declare.
DOI: 10.1039/D0NJ02631J
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2344.; d) L. Gao, W. Senevirathna and G. Sauvé Org. Lett.
2011, 13, 5354-5357.
Acknowledgements
The authors acknowledge Thales LAS company for financial
support and for the grant to S.D.
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