Effective modulation of the photoluminescence properties of 2,1,3-benzothiadiazoles and 2,1,3-benzoselenadiazoles by Pd-catalyzed C-H bond arylations

Article abstract of DOI:10.1039/c7tc05395a

A one step procedure towards the synthesis of 4-aryl-2,1,3-benzothiadiazoles, 4,7-diaryl-2,1,3-benzothiadiazoles and 4-aryl-2,1,3-benzoselenadiazoles using palladium-catalyzed regioselective C-H bond arylations of 2,1,3-benzothiadiazole and 2,1,3-benzoselenadiazole was developed. A donor-acceptor compound was also synthesized via two successive C-H bond arylations at C4 and C7 positions of the 2,1,3-benzothiadiazole unit. One of the major achivements of this methodology arises from the fine modulation of the fluorescence wavelength with emission colors covering blue to red regions of the visible spectrum by the simple introduction of the suitable aryl group on the 2,1,3-benzothiadiazole unit.

Full text of DOI:10.1039/c7tc05395a

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DOI: 10.1039/C7TC05395A.
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Nguyên T. K. Thanh, Xiaodi Su et al.
Fine-tuning of gold nanorod dimensions and plasmonic properties using
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ARTICLE
Effective Modulation of 2,1,3-Benzothiadiazoles and 2,1,3-
Benzoselenadiazoles Photoluminescence Properties by Pd-
Catalyzed C–H Bond Arylations
Received 00th January 20xx,
Accepted 00th January 20xx
Imane Idris,a, b Thibault Tannoux,a Fazia Derridj,b Vincent Dorcet,a Julien Boixel,a,* Veronique
Guerchais,a Jean-François Soulé, a,* and Henri Douceta
DOI: 10.1039/x0xx00000x
www.rsc.org/
A
one step procedure towards 4-aryl-2,1,3-benzothiadiazoles, 4,7-diaryl-2,1,3-benzothiadiazoles and 4-aryl-2,1,3-
benzoselenadiazoles using palladium-catalyzed regioselective C–H bond arylations of 2,1,3-benzothiadiazole and 2,1,3-
benzoselenadiazole was developed. A donor–acceptor compound was also synthetized via two successive C–H bond
arylations at C4 and C7 positions of the 2,1,3-benzothiadiazole unit. One of the major achivement of this methodoly refer
from the fine modulation of the fluorescence wavelength with emission colors covering the blue to the red part of the
visible spectrum by the simple introduction of the suitable aryl group on the 2,1,3-benzothiadiazole unit.
Introduction
Organic functional materials are finding more and more
applications. Among them π-systems of polycyclic aromatic or
heteroaromatic compounds such as 2,1,3-benzothiadiazole
and 2,1,3-benzoselenadiazole are being actively investigated
as cheap replacement of traditional inorganic semiconductors
for the development of organic light-emitting diodes (OLED),1
organic photovoltaics (OPV)2 and bioprobes for bioimaging
Figure 1. Examples of Useful Molecules Containing 4-Aryl-Benzothiadiazole or 4-Aryl-
analyses.3
These strong electron acceptor heterocycles
Benzoselenadiazole Units.
represent a pivotal framework for the construction of organic
donor−acceptor (D−A) dyes.4 As example, in 2005, Ho and co-
Despite these wide applications of 4-aryl-substituted 2,1,3-
benzoselenadiazoles and 2,1,3-benzoselenadiazoles, their
synthesis remains challenging and often requires multi-steps
workers developed a new class of organics dyes (compound
based on benzothiadiazole and benzoselenadiazole
chromophores, which display good power conversion
I)
a
synthesis.
palladium catalyzed Suzuki,7 Stille,8 or Hiyama7a,
Protocols involving bromination followed by
9
efficiency (Figure 1, left).5 Benzothiadiazoles are also used as
acceptor units in donor acceptor (D–A) conjugated polymers,
such as the polymer solar cell II (Figure 1, middle).6
cross-
coupling reactions are the most commonly employed (Figure
2a). Negishi reactions using an organozinc reagent prepared
from benzofurazan through a magnesiation with bis(2,2,6,6-
tetramethylpiperidin-1-yl)magnesium–lithium
chloride
complex (TMP2Mg·2LiCl) followed by transmetalation with zinc
chloride, have also been reported (Figure 2b).10 Since the
discovery by Nakamura11 and Otha12 of the Pd-catalyzed C–H
bond arylation of heteroarenes using aryl halides, this
methodology has emerged as one of the most reliable for the
eco-friendly formation of C–C bonds for the access to a wide
variety of arylated heterocycles.13 In 2013, Marder and co-
workers reported the first example of C–H bond activation of
5,6-difluoro-2,1,3-benzothiadiazole using 10 mol% Pd(OAc)2
associated to 20 mol% di-tert-butyl(methyl)phosphonium
tetrafluoroborate (Figure 2c).14
However, 2,1,3-
benzothiadiazole was not reactive under these reactions
conditions, demonstrating the huge impact of fluorine atom in
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Figure 2. Previous Strategies to Synthetize 4-Aryl 2,1,3-Benzothiadiazoles and 2,1,3-
Pd-catalyzed C–H arylations via concerted-metalation
deprotonation pathway.15 This C–H bond protocol was then
applied in polymerization using dibromobenzene derivatives,16
and for the synthesis of organic dyes containing electron-rich
(donor) and electron-poor (acceptor) sections.17 An example
of direct arylation at C4 position of 5-fluoro-2,1,3-
benzothiadiazole has also been reported.18 Latter, Marder
and co-workers extended the substrate scope to other
electron deficient 2,1,3-benzoselenadiazoles such as 5,6-
dicyano- and 5,6-dinitro-substituted ones (Figure 2d).19 To our
knowledge there is no report on direct arylation, via a metal-
catalyzed C–H bond activation, of unsubstituted 2,1,3-
benzothiadiazole and 2,1,3-benzoselenadiazoles. Recently, we
disclosed that phosphine-free palladium acetate catalyzes the
C–H bond arylation of benzofurazan (Figure 2e).20 Therefore,
we decided to investigate the reactivity of unsubstituted 2,1,3-
benzothiadiazole and 2,1,3-benzoselenadiazole in palladium-
catalyzed C–H bond arylation for the straightforward access to
Benzoselenadiazoles
Results and Discussion
Based on our recent results on palladium-catalyzed direct
arylation of benzofurazan using aryl bromides as aryl source,20
we examined the reactivity of 2,1,3-benzothiadiazole (Table 1).
Using our previously reported reaction conditions, namely 1
mol% Pd(OAc)2 in the presence of KOAc in DMA at 120 ºC, no
reaction occurred between 2,1,3-benzothiadiazole and 4-
bromobenzonitrile (Table 1, entry 1). Using a higher reaction
temperature (i.e. 150 ºC), arylated 2,1,3-benzothiadiazole 1,
resulting from C–H bond activation at the C4 position, was
obtained in 52% yield (Table 1, entry 2). When the reaction
was performed in the presence of K2CO3 as base, no reaction
occurred; while the used of potassium pivalate (PivOK) and
potassium adamantane-1-carboxylate (AdCO2K) allowed the
4-arylated
2,1,3-benzothiadiazoles
and
2,1,3-
formation of
1 in 84% and 65% yields, respectively. Other
benzoselenadiazoles (Figure 2e).
palladium sources were evaluated (Table 1, entries 6-8). PdCl2
displayed a similar reactivity than Pd(OAc)2, as the arylated
product
Palladium dimer complex [Pd(C3H5)Cl]2 gave a slightly lower
yield in of 72% (Table 1, entry 7). A diphosphine palladium
1 was isolated in 82% yield (Table 1, entry 6).
1
catalysts such as PdCl(C3H5)(dppb) did not allow to increase
the yield compared to phosphine-free procedure (Table 1,
entry 8).
Table 1. Optimization of the Reaction Conditions
Entry
[Pd]
Base
T (ºC)
Yield in 1
(%)[a]
1
2
3
4
5
6
7
8
Pd(OAc)2
Pd(OAc)2
KOAc
KOAc
120
150
150
150
150
150
150
150
0
52
0
Pd(OAc)2
K2CO3
PivOK
AdCO2K
PivOK
PivOK
PivOK
Pd(OAc)2
84
65
82
77
76
Pd(OAc)2
PdCl2
[Pd(C3H5)Cl]2
PdCl(C3H5)(dppb)
[a] isolated yield
With the best conditions in hands, namely 1 mol% phosphine-
free Pd(OAc)2 associated to PivOK as base in DMA at 150 ºC,
we payed close attention to the scope of the reaction (Scheme
1). First, we examined the reactivity of para-substituted aryl
bromides.
bromobenzaldehyde,
bromopropiophenone and 4-bromobenzophenone reacted
nicely to deliver the 4-arylated 2,1,3-benzothiadiazoles in
65–74% yields. 1-Bromo-4-chlorobenzene displayed a lower
reactivity, as the desired product was isolated in only 55%
Electron-deficient 4-bromonitrobenzene, 4-
ethyl 4-bromobenzoate, 4-
2–6
7
yield, due to the formation of a side product arising from the
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homocoupling of this aryl bromide. It should be noted that bromo-4-chlorobenzene and
ARTICLE
1
equivalent of 2,1,3-
under these reaction conditions, the C–Cl bond did not react. benzothiadiazole in the presence of
1 mol% Pd(OAc)2
Bromobenzene, 1-bromo-4-(tert-butyl)benzene and 4- associated to 3 equivalents of PivOK in DMA at 150 ºC, we
bromoanisole have been successfully employed using this were pleased to isolate 4,7-bis(4-chlorophenyl)-2,1,3-
phosphine-free palladium coupling to give
yields. A meta-substituent on the aryl bromide had almost no 1-bromo-3-(trifluoromethyl)benzene
effect, as the desired arylated products 11 14 were obtained bis(trifluoromethyl)benzene, the
8
–
10 in 60%–65% benzothiadiazole (24) as the major product in 64% yield. From
and 1-bromo-3,5-
4,7-bis(aryl)-2,1,3-
–
in good yields from 3-bromobenzonitrile, 1-bromo-3- benzothiadiazoles 25 and 26 were synthetized in good yields.
(trifluoromethyl)benzene, 3-bromonitrobenzene, and 1- The regioselectivity of the diarylation was confirmed by X-ray
bromo-3-chlorobenzene.
sensitive to the steric hindrance, as ortho-substituted aryl
bromides such as 2-bromobenzonitrile, and 2-
The reaction was almost not diffraction analysis of 26 [21]
.
bromobenzaldehyde afforded the desired products 15 and 16
in good yields. 1,3-Benzodioxol motif has been introduced on
the 2,1,3-benzothiadiazole 17, which was isolated in 45% yield
from 2,1,3-benzothiadiazole and 5-bromo-1,3-benzodioxole.
Then, in order to show the potential of this method for the
preparation of organic materials, we employed some
extended aryl bromides as coupling partners.
-
2-
Bromonaphthalene was efficiently coupled with 2,1,3-
benzothiadiazole affording 18 in 60% yield. Its X-ray diffraction
analysis confirmed the structure.21 3-Bromofluorene and 1-
bromopyrene smoothly reacted allowing the formation of the
4-arylated 2,1,3-benzothiadiazoles 19 and 20 in 56% and 43%
yields, respectively. N-containing heteroaryl bromides (e.g., 2-
Scheme 2. Scope of Aryl Bromides in Palladium-Catalyzed C4,C7 Diarylation of 2,1,3-
Benzothiadiazole.
bromo-6-methoxypyridine,
(trifluoromethyl)pyridine, or 3-bromoquinoline) also nicely
reacted to afford the desired products 21 23 in good yields.
2-bromo-6-
Using this methodology, we also carried out the
straightforward synthesis of an unsymmetrical 4,7-diaryl-2,1,3-
benzothiadiazole via two successive Pd-catalyzed C–H bond
arylations (Scheme 3). Starting from 17, a second arylation
using 1-bromo-3,5-bis(trifluoromethyl)benzene afforded the
4,7-unsymmetrical diaryl 2,1,3-benzothiadiazole 28 in 38%
yield, which should display push-pool properties.
–
Scheme 3. Example of Synthesis of
a “Push-Pull” 4,7-Unsymmetrical Diaryl 2,1,3-
benzothiadiazole by Iterative Palladium-Catalyzed C–H Bond Arylations
Syntheses of selenium containing compounds and the further
utilization of these compounds in organic synthesis for the
preparation of organic materials attracted less attention.22
While a wide variety of thiadiazole containing compounds are
known, on the contrary, a limited number of selenadiazoles
containing compounds have been prepared.23 Therefore, we
turned our attention to the reactivity of 2,1,3-
benzoselenadiazole in Pd-catalyzed C–H bond arylation
(Scheme 4). For these reactions, we employed the same
reaction conditions than for direct arylation of 2,1,3-
benzothiadaziole, namely, 1 mol% Pd(OAc)2 associated with
PivOK as base in DMA at 150 ºC. Using 4-bromobenzonitrile, 1-
Scheme 1. Scope of Aryl Bromides in Palladium-Catalyzed Direct C4 Arylation of 2,1,3-
Benzothiadiazole
Next, we investigated the formation of symmetrical 4,7-diaryl-
2,1,3-benzothiadiazoles (Scheme 2). Using 3 equivalents of 1-
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bromo-4-(tert-butyl)benzene
and
1-bromo-3,5- whole spectrum, due to additional 1(π-π*) transitions of this π-
bis(trifluoromethyl)benzene, we successfully prepared the 4- extended system but with no significant shift of the absorption
aryl-2,1,3-benzoselenadiazoles 28 30 in 52-57% yields. The bands. Similarly, replacing the fluorenyl (19) by a pyrenyl
regioselectivity of the arylation of 2,1,3-benzoselenadiazole group (20), gives rise to very intense absorption bands in the
was confirmed by X-ray diffraction analysis of 30 [21]
It should UV region, the absorption profile of the benzothiadiazole core
–
.
be noted that the reactions with 2,1,3-benzoselenadiazole are being overlapped by the intense and well-resolved absorption
more sluggish than the reactions with 2,1,3-benzothiadiazole bands of the pyrene moiety. The pyrene moiety in 20 induces
giving some unidentified decomposition products, which might a small red-shifted of the CT band (ꢀλ = 15 nm), compared
explain that arylated products are obtained in lower yields.
with the fluorene substituent in 19
.
Based on previous
experimental and theoretical studies of benzothiadiazole
derivatives, the observed spectral changes by incorporation of
various aromatic substituents can be interpreted as
a
modification of the highest-occupied molecular orbital
(HOMO) while the lowest-unoccupied molecular orbital
(LUMO), centered on the core, stays almost unchanged.24c In
other words, increasing the electron-richness (17) and/or
extension of the π-system (19
energy level resulting in a decrease of the HOMO-LUMO gap
with respect to As far as the di-substituted 2,1,3-
benzothiadiazoles are concerned, compounds 24 bearing two
p-chlorophenyl and 26 having with two 3,5-
bis(trifluoromethyl)aryl groups, exhibit similar absorption
profiles with a blue-shift of the charge-transfer band in 24
, 20) destabilize the HOMO
9.
Scheme 4. Scope of Aryl Bromides in Palladium-Catalyzed Direct C4 Arylation of 2,1,3-
,
Benzoselenadiazole
compare to 26, attributed to the strong electron-withdrawing
CF3 groups (Figure 4). As expected, the compound 27 shows
the lowest-energy CT band centered at 400 nm, due to the
presence of both electron-donating dioxole substituent and
electron-accepting (CF3)2-Ar) and benzothiadiazole groups,
which give rise to strong charge-transfer transitions.
Finally, in order to determine the interest of these new
compounds as chromophores, preliminary photophysical
studies have been conducted. UV-visible absorption spectra of
the mono-substituted
26 27 2,1,3-benzothiadiazoles, and the benzoselenadiazole
derivative 29 were recorded in dichloromethane solution at
room temperature, (see Figures and 4) and the
9, 17, 19, 20 and the di-substituted 24,
,
Table 2. Photophysical Data of the Investigated Compounds.
Emission at 298 Ka
3
Absorption
λabsa/nm (ε 103/M-1cm-1)
306 (5.8), 316 (7.0), 358
(3.0)
λema/nm
φa,b
corresponding data are summarized in Table 2. As common
feature for all the investigated compounds, their electronic
absorption spectra exhibit characteristic set of absorption
bands for benzothiadiazole and benzoselenadiazole
derivatives, with intense and well-resolved absorption bands in
the UV region, from 250 to 350 nm, together with a
moderately intense and broad absorption band tailing up in
the visible region of the spectrum. The mono-substituted
9
468
0.88
0.79
0.90
nd
17
19
20
266 (7.2), 308 (6.1), 318
(5.7),376 (2.3)
530
510
284 (19.4), 306 (18.2),
316 (15.7),376 (7.5)
268 (24.7), 378 (39.0),
316 (24.8), 326 (28.4),
344 (36.9), 382 (6.3)
270 (11.7), 320 (3.3), 384
(1.9)
530 d
2,1,3-benzothiadiazole
substituent is considered as a reference compound for the
studied series.24 The absorption spectrum of
shows, in the
9, bearing a tert-butyl group on the aryl
24
26
27
29
492
449
555
503
0.53
0.89
0.19
0.42
9
UV region, a broad band centered at 250 nm and well-resolved
bands from 280 to 325 nm, while at lower energy a weaker
and broad band which tails up to 420 nm is observed (Figure
3). According to previous studies, the UV absorption bands of
272 (18.1), 312 (10.8),
320 (9.8), 362 (10.8)
291 (5.9), 318 (3.4), 400
(3.4)
arises from 1(π-π*) transitions of the p-tert-butylphenyl
250 (6.6), 333 (6.3), 383
(1.9)
9
substituent and the benzothiadiazole core, respectively.24c At
lower energy, from 325 to 420 nm, the broad absorption band
is assigned to charge transfer transition (CT) from the electron-
donating aryl substituent to the π* accepting benzothiadiazole
moiety.24c Replacing the p-tert-butylaryl substituent by the
benzodioxole in 17, red-shifts the CT transition of 50 nm, as a
result of larger electron-donating properties of the dioxole
a Measured in CH2Cl2 solution at 298 K (C ≈ 10-5 M), with 350 nm excitation. b ref
c
: Ru(bpy)3Cl2. Measured in a drop casted film, from CH2Cl2 solution, λex = 350
nm.
Interestingly, the seleno-derivative 29 displays similar
absorption profile than its sulfur analogue 9, with absorption
bands corresponding to 1(π-π*) transitions on the tert-
group. In comparison with
9, the fluorene-based 2,1,3-
butylphenyl substituent of the benzoselenodiazole core and at
benzothiadiazole 19 exhibits higher absorptivity within the
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lower-energy, a moderately intense band arising from the quantum yield (
charge-transfer transition (Figure 3). Notably, compared with law. Compounds
the seleno-derivative 29 exhibits a large red-shift of the and 19 bearing an electron donating aryl or a fluorenyl group,
Φ
= 19 %), in agreement with the energy gap
9
and 26 display a blue emission, while 17
9
absorption bands belonging to the benzoselenodiazole core respectively, emit in the orange-red region of the spectrum.
and a moderately bathochromic effect of the CT transitions, a The benzoselenodiazole 29 displays luminescence with a
feature in agreement with previous reports on related maximum at 503 nm, red-shifted by about 35 nm with respect
benzoselenodiazole compounds.23b, 25
to the analogue 9, a feature comparable to that reported for
related benzoselenodiazole compounds.23b, 25
40000
30000
20000
10000
0
9
17
19
20
29
Photograph of 2,1,3-Benzothiadiazole Derivatives in CH2Cl2 Solution under
350 nm Irradiation
250
300
350
400
450
500
λ / nm
2000000
Figure 3. Absorption Spectra in CH2Cl2 at 298 K (C ≈ 10-5 M) of the Mono-Substituted
Compounds 9 (red line), 17 (blue line), 19 (green line), 20 (black line) and 29 (red
dotted line).
9
17
19
20
24
26
27
29
20000
15000
24
26
10000
27
5000
0
370
420
470
520
λ / nm
570
620
670
0
250
300
350
400
450
500
λ / nm
Figure 5. Emission Spectra in CH2Cl2 at 298 K (C ≈ 10-5 M) of 9 (red line), 17 (orange
line), 19 (pink line), 20 (black line), 24 (green line), 26 (blue line), 27 (brown line) and 29
(red dotted line), with λex = 350 nm.
Figure 4. Absorption Spectra in CH2Cl2 at 298 K (C ≈ 10-5 M) of the Di-Substituted
Compounds 24 (blue line), 26 (black line) and 27 (red line).
The emission spectra of 9, 17, 19, 20, 24, 26, 27 and 29 are
Note that compound 20 is non-emissive in fluid solution. This
behavior can be explained by the presence of the pyrenyl
group since pyrenes are known to be subject to self-quenching
through the formation of aggregates or excimers in solution.
Interestingly, the luminescence of 20 can be turned-on in the
solid state. The solid-state fluorescence, measured on a drop
casted film at 298 K (from dichloromethane solution), is
characterized by a broad emission band centered at 530 nm,
likely originated from the excimer state (Figure 6).26
shown in Figure 5 and the emission data are compiled in Table
2. Except compound 20, all investigated compounds are
strongly emissive in dichloromethane solution at room
temperature. Remarkably, they exhibit good to excellent
photoluminescence quantum yield (Φ) in solution as high as 90
% (19), whatever the nature of the substituent. Interestingly,
the emission color goes from the blue (λem = 449 nm for 26) to
the red (λem = 555 nm for 27) part of the spectrum, strongly
depending on the nature of the incorporated aryl group on the
benzothiadiazole core. The emission wavelength is fine-tuned
by changing the electronic richness of the system and/or by
introducing an extended π-system (fluorene, pyrene), as well
as by replacing the sulfur atom by Se (9 vs. 29). The emission
can be controlled by the CT transitions. For instance, the
multi-polar derivative 27 displays the more red-shifted
emission, consistently with CT absorption bands at lower-
energy.
However, this red-shifted fluorescence is
accompanied with a decrease of the photoluminescence
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400
450
500
550
λ / nm
600
650
Figure 6. Emission Spectrum of 20 in a Drop Cast Film from CH2Cl2 solution, with λex
=
350 nm.
Conclusions
In
summary,
2,1,3-benzothiadiazole
and
2,1,3-
benzoselenadiazole can be efficiently arylated at C4/C7
positions via palladium catalyzed C–H bond activation. Simple
phosphine-free palladium acetate associated to KOAc as base
in DMA was found to be the best reaction conditions. A wide
range of functions such as methoxy, chloro, formyl, propionyl,
benzoyl, ester, nitrile, trifluoromethyl or nitro on the aryl
bromide is tolerated. Some sterically hindered, π-extended
and heteroaromatic aryl bromides have also been employed
successfully, demonstrating the potential of this methodology
for the preparation of organic materials. Interestingly, this
method allows the introduction of aryl substituents with
different electronic properties in one step resulting in a fine
modulation of the fluorescence wavelength with emission
colors covering the blue to the red part of the visible spectrum.
The combination of these photophysical effects make such
materials especially interesting for photovoltaic and OLED
applications.
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Conflicts of interest
There are no conflicts to declare.
Acknowledgements
We thank the Algerian “Ministry of Higher Education and
Scientific Research” for a fellowship to I.I. We thank CNRS and
“Rennes Metropole” for providing financial support.
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