Dyes and Pigments xxx (2016) 1e10

Contents lists available at ScienceDirect

Dyes and Pigments

journal homepage: www.elsevier.com/locate/dyepig

2,1,3-Benzothiadiazole-based fluorophores. Synthesis,

electrochemical, thermal and photophysical characterization

sar Valdivia Martínez a, Jose
Tiago Elias Allievi Frizon a, Julio Ce
Luiz Westrup a,
Rodrigo da Costa Duarte b, Eduardo Zapp c, Kelvin Guessi Domiciano c,
Fabiano Severo Rodembusch b, Alexandre Gonçalves Dal-Bo
a, *
a
ria, 1105, CP 3167, CEP 88806-000, Criciúma, SC, Brazil
Universidade do Extremo Sul Catarinense, Av. Universita
b
Grupo de Pesquisa em Fotoquímica Orga ^nica Aplicada, Instituto de Química/UFRGS, Av. Bento Gonçalves, 9500, CEP 91501-970, Porto Alegre, RS, Brazil
c
Universidade Federal de Santa Catarina, UFSC e Campus Ararangua
, Rodovia Governador Jorge Lacerda, 3201 e Km 35,4, Jardim das Avenidas, CEP
88906072, Ararangua
, SC, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: Three photoactive compounds with p-extended conjugation based on the 2,1,3-benzothiadiazole unit
Received 31 March 2016 were synthesized and characterized. The compounds exhibited absorption in the violet-blue region with
Received in revised form molar absorptivity coefficients and radiative rate constants arising from spin and symmetry allowed 1pp*
1 July 2016
electronic transitions. An emission located in the green region with a large Stokes shift was observed,
Accepted 6 July 2016
Available online xxx
which was most likely due to a charge-transfer mechanism in the excited state. In spin-coated films a
dependence on the fluorescence emission intensity with the size of the alkoxy chain could be observed,
where an effective non-radiactive channel seems to be present to deactivate the excited state. The
Keywords:
2,1,3-Benzothiadiazole
thermal properties were analyzed by differential scanning calorimetry (DSC), and all final compounds
Quadrupolar compounds exhibited a similar behavior with a crystal-isotropic liquid transition during the heating scan and
Photophysics isotropic liquid-crystal transition during the cooling process. Thermogravimetric analysis indicated a
Fluorescence main thermal event with an initial decomposition temperature that was higher than 340
C. The elec-
Solvatochromism trochemical characterization indicate that the compounds exhibited a reversible peak at 1.48 V and an
irreversible oxidation process at 0.94 V versus Ag/Agþ. The electrochemical band gap was calculated to be
approximately 2.30 eV versus NHE. The spectroelectrochemical measurements demonstrated changes in
the absorption spectra due to changes in the electronic structure of the conjugated molecules under
oxidative and reductive potentials.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction compound is widely used as a constituent in p-conjugated systems

In recent decades, interest in new organic fluorophores that are
metal free and typically modeled on the D-p-A-p-D-type systems
has increased due to numerous advantages, such as the diversity of
molecular structures, high extinction coefficients molar, simple
synthesis, low cost, environmental issues and application in dye-
sensitized solar cells (DSSCs) [1e3].
The combination of electron-donating aromatic groups with
electron receptors systems, such as 2,1,3- benzothiadiazole, leads to
joint fluorophores with a conjugated p-adjustable wavelength,
efficient fluorescence and high electron affinity [4]. Therefore, this
* Corresponding author.

).
E-mail address: adalbo@unesc.net (A.G. Dal-Bo
to improve the electron transport ability and electroluminescence
in organic photovoltaic cells (OPVs) [5e12], organic light-emitting
diodes (OLEDs) [5,13e16], organic field-effect transistors (OFETs)
[7], organic thin film transistors (OTFTs) [5,17e21], among others
[5,7,22].
As previously reported in the literature a 2,1,3-benzothiadiazole
based compound bearing alkylated tetrazoles terminal groups as
electron donors connected through a p-conjugated D-p-A-p-D-
type system was synthesized [4]. This report aimed to study its
photophysical properties, as well as the thermal ones in order to
envisage potential applications as liquid crystals or opto-electronic
materials. Despite the good optical properties, any evidence of
liquid crystalline behavior was observed. In this way, due to
promising optical results reported, this work presents new

http://dx.doi.org/10.1016/j.dyepig.2016.07.011
0143-7208/© 2016 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Frizon TEA, et al., 2,1,3-Benzothiadiazole-based fluorophores. Synthesis, electrochemical, thermal and
photophysical characterization, Dyes and Pigments (2016), http://dx.doi.org/10.1016/j.dyepig.2016.07.011
2 T.E.A. Frizon et al. / Dyes and Pigments xxx (2016) 1e10
fluorophores containing the same 2,1,3-benzothiadiazole group as
the electron-acceptor unit but with flexible alkoxy chains, which
could lead to liquid crystalline properties, as already reported in
similar compounds [23]. The alkyl chains containing a variable
number of carbon atoms was chosen in order to study the influence
of the alkyl chain on the electron displacement toward the ben-
zothiadiazole heterocycle. If present in these structures, this
behavior could favors the electronic conductivity of these com-
pounds as already confirmed by a smaller band gap observed in
similar compounds [4], which is of great interest for technological
applications. In addition this work also aimed to study liquid
crystalline properties, since liquid crystals containing triple bonds
and long alkoxy chains have been presented [23e25]. As already
discussed in the literature, liquid crystals containing carbon triple
bonds are very interesting materials for reasons such as their large
birefringence [23,26]. Additionally, the thermal, electrochemical
and photophysical properties of the synthesized molecules were
investigated.
2. Experimental
2.1. Materials and methods
All of the reagents were used as received. The solvents were
dried and distilled prior to use based on previously reported pro-
cedures [27]. The reactions were monitored by TLC using Silica Gel
60 F254. Detection was achieved by exposure to iodine vapors or
using a sulfuric acid solution with waterproof charring. The FTIR
spectra (400-4000 cm1) were recorded on a Shimadzu IR Prestige-
21 with a resolution of 4 cm1 using KBr pellets. The 1H and 13C
NMR spectra were recorded in DMSO-d6, MEOD or CDCl3 at 400 and
100 MHz, respectively. The chemical shifts (d) are reported in parts
per million (ppm) relative to TMS (0.00 ppm), and the coupling
constants J are reported in hertz (Hz). Spectroscopic grade solvents
were used in the photophysical study. The UVeVis absorption
spectra were acquired on a Shimadzu UV-2450 spectrophotometer,
and the steady-state fluorescence spectra were measured on a
Shimadzu spectrofluorometer model RF-5301PC. Films were pre-
pared in glass substrates using a solution of the fluorophores in
CHCl3 (1.0 mg mL1) through spin-coating technique (1500 rpm for
1 min) using a MBRAUN glove box model MB 200B. Elemental
analysis of compounds 9a-c were carried out using a PerkinElmer
2400 Series II CHNS/O Elemental Analyzer System.
The quantum yield of the fluorescence (FFL) was determined
using spectroscopic grade solvents with the dilute optical method.
Coumarin 343 in ethanol (FFL ¼ 0.63) was used as the quantum
yield standard [28]. The absorption spectra of the spin-coated films
were measured on a Shimadzu UV2450PC spectrophotometer us-
ing an ISR-2200 Integrating Sphere Attachment. The baseline in the
solid state was obtained using BaSO4 (Wako Pure Chemical In-
dustries, Ltd.). The fluorescence spectra of the films were obtained
with a solid sample holder at an angle designed to limit the re-
flected excitation beam from the emission monochromator.
The electrochemical measurements were performed with a
Biologic potentiostat (Model SP-200). The cyclic voltammetry ex-
periments were performed using ca. 0.1 mg/mL solutions of 9a-c in
0.1 M tetra-n-butyl ammonium hexafluorophosphate (TBAPF6) in
dry CH2Cl2 as the supporting electrolyte, and the ferrocene/ferri-
cenium (Fc/Fcþ) redox couple was employed as the internal refer-
ence. The experiments were performed using a standard three-
electrode cell with a circular glassy carbon electrode, a Pt-wire
counter electrode and Ag/Agþ (AgNO3 0.01 M in acetonitrile) as
the reference electrode. The measurements were performed in an
electrolyte solution previously purged with purified nitrogen gas.
The spectroelectrochemical measurements were performed on a
Please cite this article in press as: Frizon TEA, et al., 2,1,3-Benzothiadiazole-based fluorophores. Synthesis, electrochemical, thermal and
photophysical characterization, Dyes and Pigments (2016), http://dx.doi.org/10.1016/j.dyepig.2016.07.011
Shimadzu UV-1800 spectrofluorophotometer. Optically transparent
gold mesh was employed as the working electrode, a platinum wire
was used as the auxiliary electrode, and Ag/Agþ was employed as
the reference electrode. Tetrabutylammonium hexa-
fluorophosphate (0.1 M in CH2Cl2) was employed as the electrolyte.
The spectra of 9 a-c were obtained by applying a constant potential
with the aid of a coupled potentiostat. The thermal properties were
investigated using differential scanning calorimetry on DSC-50 and
SDT Q600 TA Instruments using a N2 atmosphere with a flow rate of
100 mL min1 and a heating rate of 10
C min1.
2.2. Synthesis
2.2.1. 1,2-Bis(dodecyloxy)benzene (2a) [29]
To a solution of catechol 1 (15 g, 135 mmol) in potassium car-
bonate (75.5 g, 546.5 mmol) and DMF (150 mL), 1-bromododecane
(65.8 mL, 273.9 mmol) was added, and the mixture was stirred at
90
C for 24 h. In addition, 250 mL of water were added, and the
organic layer was separated. Then, the aqueous layer was extracted
with 3  50 mL of dichloromethane. The extract was dried over
MgSO4 and concentrated under vacuum to afford a residue that was
recrystallized from ethanol to afford compound 2a. Yield: 85%.
Melting point: 46e48
C. 1H NMR (CDCl3, 400 MHz, d ppm): 6.92 (s,
4H), 4.04e4.00 (t, 4H, J ¼ 6.4 Hz), 1.87e1.82 (m, 4H), 1.50e1.30 (m,
36H), 0.94e0.89 (m, 6H). 13C NMR (CDCl3, 100 MHz, d ppm): 149.3,
121.0, 114.1, 69.3, 31.9, 29.7, 29.7, 29.4, 26.1, 22.7, 14.1. FTIR (vmax/
cm1): 2920, 2846, 1593, 1508, 1465, 1257, 1222, 1122, 732.
2.2.2. 1,2-Bis(decyloxy)benzene (2b)
1,2-Bis(decyloxy)benzene 2b was obtained using the same
experimental procedure as that used to synthesize compound 2a.
The extract was dried over MgSO4 and concentrated under vacuum
to yield a residue that was recrystallized from ethanol to afford
compound 2b. Yield: 83%. Melting point: 40e42
C. 1H NMR (CDCl3,
400 MHz, d ppm): 6.90 (s, 4H), 4.02e3.98 (t, 4H, J ¼ 6.4 Hz),
1.87e1.80 (m, 4H), 1.51e1.29 (br, 28H), 0.92e0.87 (m, 6H). 13C NMR
(CDCl3, 100 MHz, d ppm): 149.2, 120.9, 114.1, 77.4, 69.3, 31.9, 29.6,
29.4, 26.0, 22.7, 14.1. FTIR (vmax/cm1): 2918, 2843, 1590, 1510, 1463,
1255, 1225, 1120, 736.
2.2.3. 1,2-Bis(octyloxy)benzene (2c)
1,2-Bis(octyloxy)benzene 2c was obtained using the same
experimental procedure as that used to synthesize compound 2a.
The extract was dried over MgSO4 and concentrated under vacuum
to yield a residue that was recrystallized from ethanol to afford
compound 2c. Yield: 81%. Melting point: 23e25
C. 1H NMR (CDCl3,
400 MHz, d ppm): 6.93 (s, 4H), 4.06e4.02 (t, 4H, J ¼ 6.4 Hz),
1.92e1.82 (m, 4H), 1.54e1.34 (m, 20H), 0.96e0.91 (m, 6H). 13C NMR
(CDCl3, 100 MHz, d ppm): 149.3, 121.0, 114.1, 77.2, 69.3, 31.9, 29.5,
29.4, 26.2, 22.8, 14.2. FTIR (vmax/cm1): 2916, 2845, 1592, 1512,
1465, 1255, 1226, 1121, 736.
2.2.4. 1,2-Bis(dodecyloxy)-4-iodobenzene (3a) [30]
A mixture containing 1,2-bis(dodecyloxy-benzene) 2a (10 g,
24.1 mmol), iodine (2.83 g, 11.15 mmol) in 300 mL of glacial acetic
acid, 100 mL of water and 8 mL of sulfuric acid was heated to 40
C,
and 0.5 g of iodic acid was added. The solution was stirred at 40
C
for 1 h, and then, a second fraction of 0.5 g iodic acid was added.
After 1 h, a third portion of 0.5 g iodic acid was added. The solution
was allowed to stir for 1.5 h at 40
C. Upon cooling, the solution was
added to 200 mL of water and extracted with diethyl ether
(5  25 mL). The combined ether extracts were washed with
aqueous Na2CO3 and brine followed by drying (MgSO4), and the
solvent was removed under reduced pressure to afford compound
3a, which was used without purification. Yield: 68%.
 T.E.A. Frizon et al. / Dyes and Pigments xxx (2016) 1e10
2.2.5. 1,2-Bis(decyloxy)-4-iodobenzene (3b) [30]
A mixture containing 1,2-bis(decyloxy-benzene) 2b (10 g,
27.9 mmol), iodine (2.83 g, 11.15 mmol) in 300 mL of glacial acetic
acid, 100 mL of water and 8 mL of sulfuric acid was heated to 40
C,
and 0.5 g of iodic acid was added. The solution was stirred at 40
C
for 1 h, and then, a second fraction of 0.5 g iodic acid was added.
After 1 h, a third portion of 0.5 g iodic acid was added. The solution
was allowed to stir for 1.5 h at 40
C. Upon cooling, the solution was
added to 200 mL of water and extracted with diethyl ether
(5  25 mL). The combined ether extracts were washed with
aqueous Na2CO3 and brine followed by drying (MgSO4), and the
solvent was removed under reduced pressure to afford compound
3b, which was used without purification. Yield: 72%.
2.2.6. 1,2-Bis(octyloxy)-4-iodobenzene (3c) [30]
A mixture containing 1,2-bis(octyloxy-benzene) 2c (10 g,
33.1 mmol), iodine (3.0 g, 11.7 mmol) in 300 mL of glacial acetic
acid, 100 mL of water and 8 mL of sulfuric acid was heated to 40
C,
and 0.5 g of iodic acid was added. The solution was stirred at 40
C
for 1 h, and then, a second fraction of 0.5 g iodic acid was added.
After 1 h, a third portion of 0.5 g iodic acid was added. The solution
was allowed to stir for 1.5 h at 40
C. Upon cooling, the solution was
added to 200 mL of water and extracted with diethyl ether
(5  25 mL). The combined ether extracts were washed with
aqueous Na2CO3 and brine followed by drying (MgSO4), and the
solvent was removed under reduced pressure to afford compound
3c, which was used without purification. Yield: 70%.
2.2.7. 4-(3,4-Bis-dodecyloxy-phenyl)-2-methyl-but-3-yn-2-ol (4a)
[31]
To a mixture of 1,2-bis(dodecyloxy)-4-iodobenzene 3a (3 g,
5.23 mmol), Pd(PPh3)2Cl2 (0.18 g, 0.261 mmol) and CuI (0.1 g,
0.525 mmol), Et3N (40 mL) was added. 2-Methyl-3-butyn-2-ol
(0.52 g, 6.41 mmol) was added dropwise, and the mixture was
stirred at reflux for 5 h. The precipitate was filtered and purified by
column chromatography on silica gel using hexane/ethyl acetate
(9:1) as the eluent to afford compound 4a. Yield: 70%. Melting
point: 65e67
C. 1H NMR (CDCl3, 400 MHz, d ppm): 7.00 (dd, 1H,
J ¼ 1.8 Hz and 8.3 Hz), 6.96 (d, 1H, J ¼ 1.8 Hz), 6.78 (d, 1H, J ¼ 8.3 Hz),
4.01e3.97 (m, 4H), 1.84e1.81 (m, 4H), 1.63 (s, 6H), 1.49e1.29 (m,
36H), 0.92e0.89 (m, 6H). 13C NMR (CDCl3, 100 MHz d ppm): 149.6,
148.6, 124.9, 116.7, 114.8, 113.1, 92.1, 82.3, 69.2, 69.1, 65.7, 31.9, 31.6,
29.4, 26.1, 22.8, 14.2. FTIR (vmax/cm1): 3275, 2920, 2850, 1597, 1515,
1468, 1415,1246, 1213, 1132, 854, 815, 721.
2.2.8. 4-(3,4-Bis-decyloxy-phenyl)-2-methyl-but-3-yn-2-ol (4b)
To a mixture of 1,2-bis(decyloxy)-4-iodobenzene 3b (2.7 g,
5.23 mmol), Pd(PPh3)2Cl2 (0.18 g, 0.261 mmol) and CuI (0.1 g,
0.525 mmol), Et3N (40 mL) was added. 2-Methyl-3-butyn-2-ol
(0.52 g, 6.41 mmol) was added dropwise, and the mixture was
stirred at reflux for 5 h. The precipitate was filtered and purified by
column chromatography on silica gel using hexane/ethyl acetate
(9:1) as the eluent to afford compound 4b. Yield: 72%. Melting
point: 59e61
C. 1H NMR (CDCl3, 400 MHz, d ppm): 6.98 (dd, 1H,
J ¼ 2.0 Hz and 8.0 Hz), 6.95 (d, 1H, J ¼ 2.0 Hz), 6.80 (d, 1H, J ¼ 8.0 Hz),
4.02e3.97 (m, 4H), 1.85e1.80 (m, 4H), 1.63 (s, 6H), 1.50e1.30 (m,
28H), 0.93e0.88 (m, 6H). 13C NMR (CDCl3, 100 MHz, d ppm): 149.6,
148.6, 124.9, 116.7, 114.8, 113.1, 92.0, 82.3, 69.2, 69.1, 65.6, 31.9, 29.3,
29.2, 25.9, 22.7, 14.1. FTIR (vmax/cm1): 3272, 2922, 2853, 1595, 1513,
1465, 1413,1245, 1215, 1135, 855, 818, 725.
2.2.9. 4-(3,4-Bis-octyloxy -phenyl)-2-methyl-but-3-yn-2-ol (4c)
To a mixture of 1,2-bis(octyloxy)-4-iodobenzene 3c (2.41 g,
5.23 mmol), Pd(PPh3)2Cl2 (0.18 g, 0.261 mmol) and CuI (0.1 g,
0.525 mmol), Et3N (40 mL) was added. 2-Methyl-3-butyn-2-ol
Please cite this article in press as: Frizon TEA, et al., 2,1,3-Benzothiadiazole-based fluorophores. Synthesis, electrochemical, thermal and
photophysical characterization, Dyes and Pigments (2016), http://dx.doi.org/10.1016/j.dyepig.2016.07.011
3
(0.52 g, 6.41 mmol) was added dropwise, and the mixture was
stirred at reflux for 5 h. The precipitate was filtered and purified by
column chromatography on silica gel using hexane/ethyl acetate
(9:1) as the eluent to afford compound 4c. Yield: 68%. Melting
point: 49e51
C. 1H NRM (CDCl3, 300 MHz, d ppm): 6.96 (dd, 1H,
J ¼ 1.8 Hz and 8.2 Hz), 6.95 (d, 1H, J ¼ 1.8 Hz), 6.79 (d, 1H, J ¼ 8.2 Hz),
4.02e3.96 (m, 4H), 1.85e1.78 (m, 4H), 1.63 (s, 6H), 1.50e1.31 (m,
20H), 0.93e0.88 (m, 6H). 13C NMR (CDCl3, 75 MHz, d ppm): 149.6,
148.6, 124.9, 116.7, 114.8, 113.1, 92.1, 82.3, 69.2, 69.1, 65.6, 31.8, 31.6,
29.4, 29.3, 29.2, 26.1, 22.7, 14.1. FTIR (vmax/cm1): 3270, 2926, 2845,
1598, 1510, 1460, 1415,1230, 1215, 1135, 855, 818, 725.
2.2.10. 1,2-Bis(dodecyloxy)-4-ethynyl-benzene (5a) [4,32]
To a mixture of 4a (2.0 g, 3.78 mmol) and NaOH (0.5 g,
12.5 mmol), toluene (40 mL) was added. The mixture was heated
under reflux for 4 h. The solution was filtered and purified by col-
umn chromatography on silica gel using hexane as the eluent to
afford compound 5a. Yield: 85%. Melting point: 41e43
C. 1H NMR
(CDCl3, 400 MHz, d ppm): 7.10e7.07 (dd, 1H, J ¼ 2.0 Hz and 8.2 Hz),
7.02 (d, 1H, J ¼ 2.0 Hz), 6.83 (d, 1H, J ¼ 8.2 Hz), 4.04e3.98 (m, 4H),
3.01 (s, 1H), 1.89e1.79 (m, 4H), 1.51e1.30 (m, 36H), 0.94e0.89 (m,
6H). 13C NMR (CDCl3, 100 MHz, d ppm): 150.1, 148.6, 125.5, 117.1,
114.1, 113.1, 84.0, 75.5, 69.2, 31.9, 29.7, 29.5, 26.1, 22.7, 14.2. FTIR
(vmax/cm1): 3298, 2920, 2850, 2102, 1597, 1512, 1465, 1413,1236,
1213, 1132, 846, 806, 721.
2.2.11. 1,2-Bis(decyloxy)-4-ethynyl-benzene (5b)
To a mixture of 4b (1.78 g, 3.78 mmol) and NaOH (0.5 g,
12.5 mmol), toluene (40 mL) was added. The mixture was heated
under reflux for 4 h. The solution was filtered and purified by col-
umn chromatography on silica gel using hexane as the eluent to
afford compound 5b. Yield: 83%. Melting point: 34e36
C. 1H NMR
(CDCl3, 400 MHz, d ppm): 7.10e7.07 (dd, 1H, J ¼ 1.8 Hz and 8.5 Hz),
7.02 (d, 1H, J ¼ 1.8 Hz), 6.83 (d, 1H, J ¼ 8.5 Hz), 4.04e3.98 (m, 4H),
3.01 (s, 1H), 1.88e1.79 (m, 4H), 1.50e1.31 (m, 28H), 0.93e0.89 (m,
6H). 13C NMR (CDCl3, 100 MHz, d ppm): 150.1, 148.6, 125.5, 120.9,
117.1, 114.0, 113.1, 83.9, 77.0, 69.2, 31.9, 29.4, 29.2, 26.0, 22.9, 22.7,
14.1. FTIR (vmax/cm1): 3296, 2931, 2852, 2109, 1590, 1510, 1455,
1418,1239, 1215 1140, 849, 810, 715.
2.2.12. 1,2-Bis(octyloxy)-4-ethynyl-benzene (5c)
To a mixture of 4c (1.57 g, 3.78 mmol) and NaOH (0.5 g,
12.5 mmol), toluene (35 mL) was added. The mixture was heated
under reflux for 4 h. The solution was filtered and purified by col-
umn chromatography on silica gel using hexane as the eluent to
afford compound 5c. Yield: 80%. 1H NMR (CDCl3, 300 MHz, d ppm):
7.07 (dd, 1H, J ¼ 1.8 Hz and 8.5 Hz), 7.00 (d, 1H, J ¼ 1.8 Hz), 6.80 (d,
1H, J ¼ 8.5 Hz), 4.01e3.95 (m, 4H), 2.98 (s, 1H), 1.86e1.77 (m, 4H),
1.49e1.29 (m, 20H), 0.92e0.87 (m, 6H). 13C NMR (CDCl3, 75 MHz,
d ppm): 150.1, 148.7, 125.5, 117.1, 114.1, 113.1, 83.9, 75.4, 69.2, 31.8,
29.4, 29.3, 26.0, 22.7, 14.1. FTIR (vmax/cm1): 3292, 2938, 2856, 2102,
1594, 1519, 1459, 1416,1232, 1213 1146, 845, 819, 712.
2.2.13. Benzo[1,2,5]thiadiazole (7) [4]
Benzo [1,2,5]thiadiazole 7 was synthesized according to a pre-
viously reported protocol [4]. Yield: 86%. Melting point: 43e44
C.
1
H NMR (CDCl3, 400 MHz, d ppm): 7.97 (dd, 2H, J ¼ 3.1 Hz and
6.6 Hz); 7.56 (dd, 2H, J ¼ 3.1 Hz and 6.6 Hz). 13C NMR (CDCl3,
100 MHz, d ppm): 154.7; 129.2; 121.5. FTIR (vmax/cm1): 3088,
3053, 1613.
2.2.14. 4,7-Dibromobenzo[1,2,5]thiadiazole (8) [4]
4,7-Dibromobenzo [1,2,5]thiadiazole 8 was synthesized ac-
cording to the procedure previously described in the literature [4].
Yield: 84%. Melting point: 187e188
C. 1H NMR (CDCl3, 400 MHz,
4 T.E.A. Frizon et al. / Dyes and Pigments xxx (2016) 1e10
d ppm): 7.71 (s, 2H). 13C NMR (CDCl3, 100 MHz, d ppm): 152.9, 132.3,
113.8. FTIR (vmax/cm1): 3078, 3045, 1634.
2.2.15. 4,7-Bis-(3,4-bis-dodecyloxy-phenylethynyl)-benzo[1,2,5]
thiadiazole (9a) [4,29,33]
Dry Et3N (50 mL), 4,7-dibromo-2,1,3-benzothiadiazole 8 (0.15 g,
0.51 mmol), CuI (0.004 g, 0.02 mmol), triphenylphosphine (C6H5)3P
(0.005 g, 0.02 mmol) and Pd(PPh3)2Cl2 (0.025 g, 0.02 mmol) were
placed in a flask and degassed with argon. Next, 1,2-
bis(dodecyloxy)-4-ethynyl-benzene 5a (0.51 g, 1.1 mmol) was
added, and the mixture was maintained at 50
C for 18 h. Then, the
solvent was evaporated to dryness, and the crude product was
purified by column chromatography on silica gel using hexane/
dichloromethane (7:3) the eluent to afford compound 9a. Yield:
75% (yellow crystals). Melting point: 133e135
C. 1H NMR (CDCl3,
400 MHz, d ppm): 7.78 (s, 2H), 7.26e7.23 (dd, 2H, J ¼ 2.0 Hz), 7.19 (d,
2H, J ¼ 2.0 Hz), 6.90 (d, 2H, J ¼ 8.5 Hz), 4.08e4.04 (m, 8H), 1.89e1.84
(m, 8H), 1.51e1.29 (m, 72H), 0.91e0.87 (m, 12H). 13C NMR (CDCl3,
100 MHz, d ppm): 154.4, 150.4, 148.8, 132.2, 125.7, 117.1, 116.8, 114.5,
113.1, 98.1, 84.1, 77.1, 69.4, 69.1, 31.9, 29.7, 29.4, 26.0, 22.7, 14.1. FTIR
(vmax/cm1): 2922, 2850, 2200, 1597, 1514, 1465, 1419,1230, 1215
1132, 848, 813, 721. Anal. Calcd. for C70H108N2O4S: C, 78.31; H, 10.14;
N, 2.61; S, 2.99%; Anal. Found: C, 78.19; H, 10.21; N, 2.54; S, 2.89%.
2.2.16. 4,7-Bis-(3,4-bis-decyloxy-phenylethynyl)-benzo[1,2,5]
thiadiazole (9b)
Dry Et3N (50 mL), 4,7-dibromo-2,1,3-benzothiadiazole 8 (0.15 g,
0.51 mmol), CuI (0.004 g, 0.02 mmol), triphenylphosphine (C6H5)3P
(0.005 g, 0.02 mmol) and Pd(PPh3)2Cl2 (0.025 g, 0.02 mmol) were
placed in a flask and degassed with argon. Next, 1,2-bis(decyloxy)-
4-ethynyl-benzene 5b (0.46 g, 1.1 mmol) was added, and the
mixture was maintained at 50
C for 18 h. Then, the solvent was
evaporated to dryness, and the crude product was purified by
column chromatography on silica gel using hexane/dichloro-
methane (7:3) the eluent to afford compound 9b. Yield: 70% (or-
ange crystals). Melting point: 136e138
C. 1H NMR (CDCl3,
400 MHz, d ppm): 7.76 (s, 2H), 7.27e7.25 (dd, 2H, J ¼ 1.8 Hz), 7.18 (d,
2H, J ¼ 1.8 Hz), 6.88 (s, 2H), 4.07e4.03 (m, 8H), 1.88e1.82 (m, 8H),
1.52e1.30 (m, 56H), 0.92e0.89 (m, 12H). 13C NMR (CDCl3, 100 MHz,
d ppm): 154.4, 150.4, 148.8, 132.2, 125.7, 117.1, 116.8, 114.5, 113.1, 98.1,
84.1, 77.1, 69.3, 69.1, 31.9, 29.7, 29.4, 26.0, 22.7, 14.2. FTIR (vmax/
cm1): 2928, 2855, 2195, 1593, 1518, 1466, 1417,1232, 1217 1135,
845, 815, 723. Anal. Calcd. for C62H92N2O4S: C, 77.45; H, 9.64; N,
2.91; S, 3.33%; Anal. Found: C, 77.31; H, 9.70; N, 2.85; S, 3.27%.
2.2.17. 4,7-Bis-(3,4-bis-octyloxy-phenylethynyl)-benzo[1,2,5]
thiadiazole (9c)
Dry Et3N (45 mL), 4,7-dibromo-2,1,3-benzothiadiazole 8 (0.15 g,
0.51 mmol), CuI (0.004 g, 0.02 mmol), triphenylphosphine (C6H5)3P
(0.005 g, 0.02 mmol) and Pd(PPh3)2Cl2 (0.025 g, 0.02 mmol) were
placed in a flask and degassed with argon. Next, 1,2-bis(decyloxy)-
4-ethynyl-benzene 5c (0.39 g, 1.1 mmol) was added, and the
mixture was maintained at 50
C for 18 h. Then, the solvent was
evaporated to dryness, and the crude product was purified by
column chromatography on silica gel using hexane/dichloro-
methane (7:3) the eluent to afford compound 9c. Yield: 70% (orange
crystals). Melting point: 140e142
C. 1H NMR (CDCl3, 400 MHz,
d ppm): 7.78 (s, 2H), 7.29e7.25 (dd, 2H, J ¼ 2.0 Hz), 7.19 (d, 2H,
J ¼ 2.0 Hz), 6.90 (d, 2H, J ¼ 8.5 Hz), 4.08e4.04 (m, 8H), 1.91e1.82 (m,
8H), 1.60e1.32 (m, 40H), 0.92e0.89 (m, 12H). 13C NMR (CDCl3,
100 MHz, d ppm): 154.4, 150.4, 148.8, 132.2, 125.7, 117.1, 116.7, 114.5,
113.0, 98.1, 84.1, 77.0, 69.3, 69.1, 31.9, 29.7, 29.4, 26.1, 22.7, 14.1. FTIR
(vmax/cm1): 2925, 2859, 2191, 1597, 1514, 1469, 1413, 1232, 1211
1138, 846, 813, 728. Anal. Calcd. for C54H76N2O4S: C, 76.37; H, 9.02;
N, 3.30; S, 3.78%; Anal. Found: C, 76.19 1; H, 9.10; N, 3.21; S, 3.71%.
Please cite this article in press as: Frizon TEA, et al., 2,1,3-Benzothiadiazole-based fluorophores. Synthesis, electrochemical, thermal and
photophysical characterization, Dyes and Pigments (2016), http://dx.doi.org/10.1016/j.dyepig.2016.07.011
3. Results and discussion
3.1. Synthesis and spectroscopic characterization
The synthetic route for the preparation of the desired com-
pounds 9a-c is shown in Scheme 1.
The catechol 1 was alkylated to 1,2-bis(alkoxy)benzenes 2a-c as
described in the literature [29]. The iodoarenes 3a-c were obtained
in good yields (68%, 72% and 70%, respectively) from an adapted
synthetic methodology previously described [26]. The respective
aryl halides reacted with commercially available 2-methyl-3-
butyn-2-ol via a palladium-catalyzed cross-coupling (Sonoga-
shira’s coupling) [34e36] followed by protective group elimination
to afford compounds 5a-c [4,32]. In contrast, 2,1,3-benzothiadiazole
7 was obtained by condensation of o-phenylenediamine 1 with
thionyl chloride in a basic medium. In the next stage, the selective
bromination reaction of 2,1,3-benzothiadiazole 7 at positions 4 and
7 was performed, producing compound 8. The final products 9a-c
were obtained in high yields (~70%) via Sonogashira coupling re-
action between the intermediate 8 and the respective 1,2-
bis(alkoxy)-4-ethynyl-benzenes 5a-c to afford the desired com-
pounds 9a-c [4,29,33].
The reaction was monitored by FTIR spectroscopy
(Figs. S25eS36, supplementary data). For the final compound 9b
(Fig. S35), the disappearance of the characteristic band corre-
sponding to the axial deformation of ^CeH located at 3330 cm1
was observed. In addition, the presence of an intense band was
observed at 2200 cm1 due to the C^C stretching of the internal
alkyne. The same vibrational behavior was observed for com-
pounds 9a and 9c (Figs. S34 and S36, respectively).
The 1H NMR spectra contained characteristic signals of the
desired products (Figs. S1eS12). For instance, to compound 9b
(Fig. S11), seven signals were observed, and the four sets of
equivalent hydrogens related to the aromatic system located at 7.76
(s, 2H), 7.27e7.25 (dd, 2H, J ¼ 1.8 Hz), 7.18 (d, 2H, J ¼ 1.8 Hz) and
6.88 (s, 2H). The signal located at 7.76 ppm (s, 2H) corresponded to
the equivalent hydrogens of the benzothiadiazole central unit. In
the region of the aliphatic hydrogens, three sets of signals were
observed as follows: 4.07e4.03 ppm (m, 8H) corresponding to the
methylene group, between 1.88 and 1.30 ppm (m, 56H) and at
0.94e0.89 ppm (m, 12H) corresponding to the terminal methyl
group.
3.2. Photophysical characterization
The absorption spectra of 2,1,3-benzotiadiazoles 9a are shown in
Fig. 1. The relevant data from UVeVis absorption spectroscopy are
summarized in Table 1. It is important to note that the additional
compounds 9b-c exhibited similar photophysical behavior in the
same solvents. To better compare the electronic spectra or the ef-
fect of the alkoxy moieties on the electronic spectra of these
compounds, the results for all of the studied compounds in the
same media is shown in Fig. 1a. These compounds exhibited similar
photophysics in the same organic solvent (Figs. S37e38). Addi-
tionally, the electronic spectra of these compounds allowed for the
determination of the pure radiative lifetimes (t0) and the radiative
rate constants (k0e ) using the Strickler-Berg relationship [37]:
Z
1
z2:88  109 v2 εdv; (1)
t0 0
where v0 is the wavenumber of the maximum of the absorption
R
band and the integral is εdv e area under the absorption curve
from a plot of the molar absorptivity coefficient ε (M1$cm1) as a
function of the wavenumber v (cm1) related to a single electron
 T.E.A. Frizon et al. / Dyes and Pigments xxx (2016) 1e10 5

Scheme 1. Synthetic route to afford compounds 9a-c, where (i) DMF, K2CO3, RBr (R ¼ CnH2n); (ii) Acetic Acid, H2O, H2SO4, I2, HIO3; (iii) Et3N, CuI, PPh3, 2-methyl-3-butyne-2-ol,
PdCl2(PPh3)2; (iv) NaOH, toluene; (v) SOCl2, Et3N, CH2Cl2, (vi) Br2/HBR, (vii) PdCl2(PPh3)2, CuI, triphenylphosphine (C6H5)3P, Et3N.

Fig. 1. UVeVis absorption spectra for the 2,1,3-benzotiadiazole derivative 9a in different organic solvents (left). For comparison, all of the studied dyes 9a-c were studied in
dichloromethane (right).

oscillator. In this relationship, the pure radiative lifetime t0 is
defined as 1/k0e , and the oscillator strength (fe) can be obtained from
equation (2) [38]:
Z
fe z4:3  109 εdv
The 2,1,3-benzotiadiazoles (9a-c) exhibited absorption maxima
in the violet-blue region at approximately 440 nm (labs). The
observed absorption maxima is 40 nm redshifted in despite of a
previously published compound with the same p-extended fluo-
rophoric core, as expected due to the absence of the alkoxy aux-
ochrome moieties in its structure [23]. Compounds based on the
2,1,3-benzotiadiazole core with a similar p-conjugated structure
also presents absorption located in the violet region [4]. In addition,
the intense absorption band located around 300 nm was ascribed to
the 2,1,3-benzotiadiazole moiety. The molar absorptivity coefficient
(ε) values for both absorption bands as well as the calculated
radiative rate constants (k0e ) for all of the compounds indicate that
(2)
the spin and symmetry allowed electronic transitions were related
to 1pp* transitions. A small solvatochromic effect (Dlabs~7 nm) was
observed in the ground state, which was independent of the sol-
vent polarity and indicated a nearly absent charge-transfer char-
acter, as observed in a similar 2,1,3-benzotiadiazole compound [4].
A nearly constant radiative lifetime (t0~3 ns) was observed for all of
the compounds in all of the studied solvents, which most likely
indicates that after radiation absorption, these 2,1,3-

Please cite this article in press as: Frizon TEA, et al., 2,1,3-Benzothiadiazole-based fluorophores. Synthesis, electrochemical, thermal and
photophysical characterization, Dyes and Pigments (2016), http://dx.doi.org/10.1016/j.dyepig.2016.07.011
6 T.E.A. Frizon et al. / Dyes and Pigments xxx (2016) 1e10

Table 1 Table 2
Relevant photophysical data of the UVeVis spectra of 9a-c, where labs is the ab- Relevant photophysical data of the steady-state fluorescence spectra of 9a-c, where
sorption maxima (nm), ε is the molar absorptivity (104 M1 cm1), fe is the lem is the emission maxima (nm), DlST is the Stokes shift (nm/cm1) and FFL is the
calculated oscillator strength, k0e (108) is the calculated radiative rate constant (s1) fluorescence quantum yield.
and t0 is the inherent emission lifetime (ns).
Dye Solvent lem DlST FFL
Dye Solvent labs (ε) fe k0e t0
9a Toluene 530 85/3604 0.397
9a Toluene 445 (3.4) 0.642 3.24 3.08 1,4-Dioxane 540 101/4261 0.385
1,4-Dioxane 439 (2.8) 0.551 2.86 3.50 Dichloromethane 562 120/4831 0.220
Dichloromethane 442 (3.1) 0.603 3.09 3.24 9b Toluene 530 85/3604 0.387
9b Toluene 445 (3.1) 0.588 2.97 3.37 1,4-Dioxane 541 102/4295 0.362
1,4-Dioxane 439 (3.9) 0.764 3.97 2.52 Dichloromethane 563 121/4862 0.238
Dichloromethane 442 (3.2) 0.631 3.23 3.10 9c Toluene 533 88/3710 0.391
9c Toluene 445 (2.6) 0.549 2.77 3.61 1,4-Dioxane 541 102/4295 0.349
1,4-Dioxane 439 (3.0) 0.590 3.06 3.27 Dichloromethane 563 121/4862 0.237
Dichloromethane 442 (2.8) 0.545 2.79 3.59

transition, which allows for better electron delocalization in the

benzotiadiazoles populate the same excited state.
The fluorescence emission spectra of 2,1,3-benzotiadiazole 9a
are shown in Fig. 2. Compounds 9b-c exhibited a similar photo-
physical behavior in the same solvents (Figs. S39e40). In addition,
compounds 9a-c were studied in dichloromethane. A related
emission profile was observed in 1,4-dioxane and toluene (data not
shown). The emission curves were obtained by exciting the com-
pounds at the absorption maxima wavelength. The relevant data
from fluorescence emission spectroscopy are listed in Table 2,
where the solvents are presented in order of increasing dipole
moment.
The 2,1,3-benzotiadiazoles (9a-c) exhibited fluorescence emis-
sion in the green region, where the different alkoxy substituents do
not play a fundamental role in the excited state of the these fluo-
rophores. However, a solvatochromic effect was observed in the
excited state (Dlem~30 nm). A similar emission maxima was
observed in parent compounds [4,23]. With regards to the chemical
structure of these compounds, the solvatochromism as well as the
large Stokes shift (85e121 nm/3604-4862 cm1) are most likely
related to the charge-transfer character of the excited state. A larger
Stokes shift observed in these compounds in despite of the similar
one (97 nm/4122 cm1) [23] indicates that the number of alkoxy
chains in the fluorophoric unit plays an important role on the en-
ergy loss in the excited state before the radiactive decay. An in-
crease in the dipole moment of the solvent results in an emission
shift to larger wavelengths due to the nature of the electronic
excited state. Therefore, the observed photophysics can be under-
stood when a relaxed excited state is more polar in the excited state
than in the ground state. Similar values to the fluorescence quan-
tum yields were obtained for these compounds (~30%), indicating
that in solution, the presence of different alkoxy groups in the
fluorophore structure do not appear to play a significant role in the
excited singlet state deactivation channel. However, the spin-
coated films of these compounds exhibited an interesting photo-
physical behavior (Fig. 3 and Table 3).
Fig. 3 shows the diffuse reflectance UVeVis spectra of the spin-
coated films and the absorption maxima were at 443 nm. Similar to
that observed in solution, the chemical structure of the compounds
do not appear to affect the photophysics of the 2,1,3-
benzotiadiazoles in the spin-coated films in the ground state.
However, the fluorescence emission appears to be quite different
from that observed in solution, presenting a dependence on the
emission intensity with the size of the alkoxy chain. In spin-coated
films for the fluorophore containing the longest chain alkoxy, a
non-radioactive channel seems to be very effective to deactivate
the excited state, nearly quenching the fluorescence emission re-
flected in a lower fluorescence quantum yield.
3.3. Electrochemical properties
The cyclic voltammogram curves (Fig. 4, S41 and S42) exhibited
the distinct anodic and cathodic behavior. In addition, the oxidation

Fig. 2. Fluorescence emission spectra for the 2,1,3-benzotiadiazole derivative 9a in organic solvents (left). For comparison, all of the studied dyes 9a-c were studied in dichloro-
methane (right).

Please cite this article in press as: Frizon TEA, et al., 2,1,3-Benzothiadiazole-based fluorophores. Synthesis, electrochemical, thermal and
photophysical characterization, Dyes and Pigments (2016), http://dx.doi.org/10.1016/j.dyepig.2016.07.011
 T.E.A. Frizon et al. / Dyes and Pigments xxx (2016) 1e10 7

Fig. 3. DRUV spectra (left) and fluorescence emission spectra (right) of spin-coated films containing the 2,1,3-benzotiadiazole derivatives 9a-c.

Table 3 electrochemical band gaps of these compounds were calculated by

Relevant photophysical data of the UVeVis absorption and steady-state fluorescence subtracting the HOMO level from the LUMO level. The onset values
spectroscopies of 9a-c in spin-coated films, where, labs and lem are the absorption
and emission maxima, respectively, DlST is the Stokes shift and FFL is the fluores-
were estimated by taking the intersection point between the
cence quantum yield. baseline and the tangent [40]. The observed oxidation and reduc-
tion peaks of the compounds 9a-c suggests the possibility of both
Dye labs (nm) lem (nm) DlST (nm/cm1) FFL
hole and electron transport, leading to a potential application as
9a 443, 473 s 554 111/4523 0.069 electroluminescent device. This feature is very important since it
9b 443, 473 s 555 112/4555 0.470
would not be necessary to employ different molecules in the
9c 443, 473 s 553 110/4490 0.375
electron and hole-transporting layers of organic light emitting
devices [41]. Analysis of the HOMO-LUMO energy level calculations
shows that the band gaps are in good agreement with the CV data
and to the UVevis onset value. The optical and electrochemical data
obtained from these studies are summarized and compared in
Table 4.
Spectroelectrochemical measurements were performed to
investigate the changes in the absorption spectra due to changes in
the electronic structure of the conjugated molecules as the applied
voltage gradually increased [42]. The applied potentials were cho-
sen before the peak, on the peak and after the peak positions
observed during the cyclic voltammetry (Fig. 5). In the corre-
sponding spectrum obtained at the open-circuit potential (OCP)
(Fig. 5c, S43 and S44), two main absorption processes
(400e500 nm and 250e350 nm) were observed in the analyzed

Table 4
Optical and electrochemical properties of compounds 9a-c, where Eox is the onset
potential of oxidation, Ered is the onset potential of reduction, Ip (HOMO) is the
ionization potential, Ea (LUMO) is the electron affinity, Eg is the band gap and lonset is
the absorption onsets wavelength.

Fig. 4. Cyclic voltammogram of compound 9c on a glassy carbon electrode in 0.1 Parameters Compounds
TBAPF6/CH2Cl2 at 100 mV s1. The ferrocene cyclic voltammogram under the same 9a 9b 9c
conditions is shown for reference (inset).
Eox (V) vs. NHEa 1.216 1.196 1.206
Ered (V) vs. NHEa 1.154 1.174 1.134
Ip (HOMO) (eV)b 5.656 5.636 5.646
and reduction peaks were directly correlated to the electron Ea (LUMO) (eV)c 3.286 3.266 3.234
transfer at the HOMO (ionization potential) and LUMO (electron Eg (eV)d 2.370 2.370 2.312
affinity), respectively. Because Ag/Agþ was used as a reference lonset (nm)e 527 526 530
electrode, the potential was normalized to NHE using the Fc/Fcþ Eg (eV)f 2.353 2.357 2.339
couple as an internal standard [39]. The well-defined reduction a
Eox/red (vs. NHE) ¼ Eox/red (vs. Ag/Agþ) þ0.266.
process, at 1.498 V, 1.515 V and 1.485 V versus Ag/Agþ, can be
b
Ip ¼ -(Eoxþ4,44) eV.
c
attributed to reduction of the benzothiadiazole ring. In addition, at Ea ¼ -(Eredþ4,44) eV.
d
Electrochemical band gap; elonset: absorption onsets wavelength.
0.95 V, 0.93 V and 0.94 V versus Ag/Agþ a well-defined irreversible f
Optical band gap calculated on the low energetic edge of the absorption spec-
oxidation process takes place for compounds 9a-c. The trum (Eg ¼ 1240/lonset).

Please cite this article in press as: Frizon TEA, et al., 2,1,3-Benzothiadiazole-based fluorophores. Synthesis, electrochemical, thermal and
photophysical characterization, Dyes and Pigments (2016), http://dx.doi.org/10.1016/j.dyepig.2016.07.011
8 T.E.A. Frizon et al. / Dyes and Pigments xxx (2016) 1e10

Fig. 5. Spectroelectrochemistry in different potential regions for 9c: (a) reduction potential, (b) oxidation potential and (c) OCP.

region. The high-energy band may be due to simple 1pp* transi-

tions. The reduction potentials (Fig. 5a, S43 and S44) result in CT
bands with lower intensities and in the formation of new weak
transitions at lower energies 560 and 720 nm for 9a-c (Figures S45,
S46 and S47). The oxidative potentials result in lower intensities for
two main bands and the formation of new band at lower energies
for 9a-c (Fig. 5b, S43 and S44).

3.4. Thermal properties

The thermal stability of the compounds 9a-c was evaluated by

thermogravimetric analysis (TGA) (Fig. 6). To better understand the
thermal events, the DTG curves for all of the compounds were
obtained from the TGA curves. The overall degradation process
indicates a mass loss of approximately 75%. A main thermal event
was observed for the studied compounds and correspond to a mass
loss of approximately 55% at an initial decomposition temperature
Fig. 6. Thermograms (TGA) and DTG curves of compounds 9a-c.
of 340
C with a high maximum degradation rate located at
approximately 430
C. A small thermal event was detected at
approximately 550
C. This stage corresponds to a loss of 20%. been observed at approximately 600
C or higher [44e46]. There-
Surprisingly, even at 800
C, a mass residue of approximately 30% fore, we believe that the observed residue in the thermograms may
remains in the thermogram. It important to note that information be related to a polymeric structure.
regarding the thermal analysis of these types of compounds is The thermal properties were investigated by differential scan-
lacking. 1,2,3-Benzothiadiazole may lead to a polymeric structure ning calorimetry (DSC). The heating and cooling scans were con-
under heat treatment [43]. For polymers or even copolymers con- ducted using a rate of 10
C min1. To eliminate the non-intrinsic
taining the 2,1,3-benzothiadiazole unit, a residue of ca. 30% has

Please cite this article in press as: Frizon TEA, et al., 2,1,3-Benzothiadiazole-based fluorophores. Synthesis, electrochemical, thermal and
photophysical characterization, Dyes and Pigments (2016), http://dx.doi.org/10.1016/j.dyepig.2016.07.011
 T.E.A. Frizon et al. / Dyes and Pigments xxx (2016) 1e10
thermal history, second heating scans were performed (Fig. 7).
Compounds 9a-c do not exhibit thermotropic mesomorphism, as
already observed in similar compounds containing the same fluo-
rescent core but a different functional group [4], which indicate
that structural changes also play an important role on the thermal
properties of these compounds. In addition, the amount of alkoxy
groups also tailor these properties since the same fluorescent core
with similar functional group presenting only one alkoxy chain
displayed smectic C and nematic phases [23]. Similar melting
transition (Cr-I) temperatures were observed for compound 9a
(131.8
C), compound 9b (135.7
C) and compound 9c (139.7
C).
However, the heat of fusion of compound 9c was significantly
higher than those of 9a and 9b, indicating that the octoxyl group is
more beneficial to a higher melting point than the dodecyl group.
4. Conclusions
A series of D-p-A-p-D-type compounds were synthesized in
good yields and characterized. Their photophysical behaviors were
studied using absorption spectroscopy in the UVeVis region and
using time-resolved, stationary fluorescence emission. Compounds
9a-c exhibited absorption maxima at approximately 442 nm with
their molar absorptivity coefficient (ε) values being related to the
1
pp* transitions. Changes in the solvent polarity did not cause a
significant solvatochromic effect (~6 nm), indicating a nearly absent
charge-transfer characteristic in the ground state. Compounds 9a-c
exhibited emissions in the green region (532e562 nm), which were
dependent on the polarity of the solvent used, and a large Stokes
shift (90e117 nm) was observed, which was most likely due to
charge-transfer mechanism (ICT) in the excited state. The fluores-
cence emission in spin-coated films showed to be different from
that observed in solution, where a dependence on the emission
intensity with the size of the alkoxy chain was observed. For the
fluorophore containing the longest chain alkoxy, a non-radioactive
channel seems to be very effective to deactivate the excited state,
nearly quenching the fluorescence emission in this compound. The
compounds present initial decomposition temperatures around
340
C. Differential scanning calorimetry analysis indicate that
compounds 9a-c do not exhibit thermotropic mesomorphism.
Fig. 7. DSC thermograms of compounds 9a-c.
Please cite this article in press as: Frizon TEA, et al., 2,1,3-Benzothiadiazole-based fluorophores. Synthesis, electrochemical, thermal and
photophysical characterization, Dyes and Pigments (2016), http://dx.doi.org/10.1016/j.dyepig.2016.07.011
9
The values of the energy levels of the HOMO and LUMO mo-
lecular orbitals as well as the value of the optical band gap of these
compounds agree with those for similar compounds found in the
literature. The electrochemical band gaps confirmed that the en-
ergy level required for the materials is compatible for building
electronic devices.
Acknowledgements
The authors would like to thank Conselho Nacional de Desen-
volvimento Científico e Tecnolo
gico (CNPq) (440619/2014-9),
Fundaç~
ao de Amparo a Pesquisa do Estado do Rio Grande do Sul
(FAPERGS) and CELESC P&D 5697-8712/2012 for financial support.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.dyepig.2016.07.011.
References
[1] Lee DH, Lee MJ, Song HM, Song BJ, Seo KD, Pastore M, et al. Organic dyes
incorporating low-band-gap chromophores based on p-extended benzothia-
diazole for dye-sensitized solar cells. Dyes Pigm 2011;91:192e8.
[2] Seo KD, Choi IT, Park YG, Kang S, Lee JY, Kim HK. Novel D-A-p-A coumarin
dyes containing low band-gap chromophores for dye-sensitised solar cells.
Dyes Pigm 2012;94:469e74.
[3] Thomas KRJ, Singh P, Baheti A, Hsu YC, Ho KC, Lin JT. Electro-optical properties
of new anthracene based organic dyes for dye-sensitized solar cells. Dyes
Pigm 2011;91:33e43.
[4] Westrup JL, Oenning LW, Paula MMS, Duarte RC, Rodembusch FS, Frizon TEA,
et al. New photoactive D-p-A- p-D benzothiadiazole derivative: synthesis,
thermal and photophysical properties. Dyes Pigm 2016;126:209e17.
[5] Yun D, Yoo H, Heo S, Song H, Moon D, Woo J, et al. Synthesis and photovoltaic
characterization of D/A structure compound based on N-substituted pheno-
thiazine and benzothiadiazole. J Ind Eng Chem 2013;19:421e6.
[6] Fang Q, Liu Y, Lai H, Zhong H, Xu E, Du J, et al. New low band gap molecules
based on ethylene-separated benzothiadiazoles: synthesis and band gap
comparison. Tetrahedron Lett 2010;51:4462e5.
[7] Bai F, He Q, He C, Sun Y, Wu H, Li Y. Amorphous molecular material containing
bisthiophenyl-benzothiadiazole and triphenylamine with bipolar and low-
band gap characteristics for solar cells. Thin Solid Films 2008;516:5935e40.
[8] Lee JY, Kim SH, Song IS, Moon DK. Efficient donor-acceptor type polymer
semiconductors with well-balanced energy levels and enhanced open circuit
voltage properties for use in organic photovoltaics. J Mater Chem 2011;21:
16480e7.
[9] Lee JY, Song KW, Song HJ, Moon DK. Synthesis and photovoltaic property of
donor-acceptor type conjugated polymer containing carbazole and 4,7-
dithiazolylbenzothiadiazole moiety utilized as a promising electron with-
drawing unit. Synth Met 2011;161:2434e40.
[10] Lee JY, Song KW, Ku JR, Sung TH, Moon DK. Development of DA-type polymers
with phthalimide derivatives as electron withdrawing units and a promising
strategy for the enhancement of photovoltaic properties. Sol Energy Mater Sol
Cells 2011;95:3377e84.
[11] Li Y, Zou Y. Conjugated polymer photovoltaic materials with broad absorption
band and high charge carrier mobility. Adv Mater 2008;20:2952e8.
[12] Li Y, Xue L, Hui L, Li Z, Xu B, Wen S, et al. Energy level and molecular structure
engineering of conjugated donor-acceptor copolymers for photovoltaic ap-
plications. Macromolecules 2009;42:4491e9.
[13] Song IS, Heo SW, Lee JY, Moon DK. Study on the ClO”4 doped PEDOT-PEG in
organic solvent using a hole injection layer for PLEDs. J Ind Eng Chem
2011;17:651e6.
[14] Song HJ, Lee SM, Lee JY, Choi BH, Moon DK. The synthesis and electrolumi-
nescent properties of dithienylquinacridone-based copolymers for white
light-emitting diodes. Synth Met 2011;161:2451e9.
[15] Song HJ, Lee JY, Song IS, Moon DK, Haw JR. Synthesis and electroluminescence
properties of fluorene-anthracene based copolymers for blue and white
emitting diodes. J Ind Eng Chem 2011;17:352e7.
[16] Yamada S, Park S, Song S, Heo M, Shim JY, Jin Y, et al. Synthesis and charac-
terization of fluorene-carbazole and fluorene-phenothiazine copolymers with
carbazole and oxadiazole pendants for organic light emitting diodes. Polymer
2010;51:6174e81.
[17] Park MJ, Lee JH, Park JH, Lee SK, Lee JI, Chu HY, et al. Synthesis and electro-
luminescence of new polyfluorene copolymers with phenothiazine derivative.
Their application in white-light-emitting diodes. Macromolecules 2008;41:
3063e70.
[18] Jung MS, Shin W, Park SJ, You HR, Park JB, Suh HS, et al. Synthesis and
characterization of thermally cross-linkable hole injection polymer based on
10 T.E.A. Frizon et al. / Dyes and Pigments xxx (2016) 1e10
poly(10-alkylphenothiazine) for polymer light-emitting diode. Synth Met
2009;159:1928e33.
[19] Zou Y, Wu W, Sang G, Yang Y, Liu Y, Li Y. Polythiophene derivative with
phenothiazine-vinylene conjugated side chain: synthesis and its application
in field-effect transistors. Macromolecules 2007;40:7231e7.
[20] Mondal R, Becerril HA, Verploegen E, Kim D, Norton JE, Ko S, et al. Thiophene-
rich fused-aromatic thienopyrazine acceptor for donor-acceptor low band-
gap polymers for OTFT and polymer solar cell applications. J Mater Chem
2010;20:5823e34.
[21] Kim CG, Quinn JR, Facchetti A, Marks TJ. Pentacene transistors fabricated on
photocurable polymer gate dielectrics: tuning surface viscoelasticity and de-
vice response. Adv Mater 2010;22:342e6.
[22] Anant P, Mangold H, Lucas NT, Laquai F, Jacob J. Synthesis and characterization
of donor-acceptor type 4,4’-bis(2,1,3-benzothiadiazole) based copolymers.
Polymer 2011;52:4442e50.
[23] Vieira AA, Cristiano R, Bortoluzzi AJ, Gallardo H. Luminescent 2,1,3-
benzothiadiazole-based liquid crystalline compounds. J Mol Struct
2008;875:364e71.
[24] Vasconcelos UV, Dalmolin E, Merlo AA. Synthesis and thermal behavior of new
N-heterotolan liquid crystals. Org Lett 2005;7:1027e30.
[25] Paraskos AJ, Swager TM. Effects of desymmetrization on thiophene-based
bent-rod mesogens. Chem Mater 2002;14:4543e9.
[26] Wu ST, Finkenzeller U, Rieffenrath V. Physical properties of diphenyldiace-
tylenic liquid crystals. J Appl Phys 1989;65:4372e6.
[27] Armarego WLF. In: Purification of laboratory chemicals. fifth ed. Cornwall, UK:
Elsevier Academic Press; 2003. Armarego WLF, Chai CLL.
[28] Wurth C, Grabolle M, Pauli J, Spieles M, Resch-Genger U. Nat Protoc 2013;8:
1535e50.
[29] Behramand B, Molin F, Gallardo H. 2,1,3-Benzoxadiazole and 2,1,3-
benzothiadiazole-based fluorescent compounds: synthesis, characterization
and photophysical/electrochemical properties. Dyes Pigm 2012;95:600e5.
[30] Freudenmann R, Behnisch B, Hanack M. Synthesis of conjugated-bridged tri-
phenylenes and application in OLEDs. J Mater Chem 2001;11:1618e24.
[31] Valentini L, Bagnis D, Marrocchi A, Seri M, Taticchi A, Kenny JM. Novel
anthracene-core molecule for the development of efficient PCBM-based solar
cells. Chem Mater 2007;20:32e4.
[32] Cui W, Zhao Y, Tian H, Xie Z, Geng Y, Wang F. Synthesis and characterizations
of poly(9,10-bisarylethynyl-2,6-anthrylene)s and poly(9,10-bisalkynyl-2,6-
anthrylene). Macromolecules 2009;42:8021e7.
Please cite this article in press as: Frizon TEA, et al., 2,1,3-Benzothiadiazole-based fluorophores. Synthesis, electrochemical, thermal and
photophysical characterization, Dyes and Pigments (2016), http://dx.doi.org/10.1016/j.dyepig.2016.07.011
[33] Silvestri F, Marrocchi A, Seri M, Kim C, Marks TJ, Facchetti A, et al. Solution-
processable low-molecular weight extended arylacetylenes: versatile p-type
semiconductors for field-effect transistors and bulk heterojunction solar cells.
J Am Chem Soc 2010;132:6108e23.
[34] Sonogashira K. Development of Pd-Cu catalyzed cross-coupling of terminal
acetylenes with sp2-carbon halides. J Organomet Chem 2002;653:46e9.
[35] Nova
k ZP, Nemes P, Kotschy A. Tandem Sonogashira coupling: an efficient
tool for the synthesis of diarylalkynes. Org Lett 2004;6:4917e20.
[36] Chinchilla R, Na
jera C. The Sonogashira reaction: a booming methodology in
synthetic organic chemistry. Chem Rev 2007;107:874e922.
[37] Strickler SJ, Berg RA. Relationship between absorption intensity and fluores-
cence lifetime of molecules. J Phys Chem 1962;37:814e22.
[38] Turro NJ, Scaiano JC, Ramamurthy V. In: Principles of molecular photochem-
istry: an introduction. first ed. University Science Books; 2008.
[39] Haram SK, Quinn BM, Bard AJ. Electrochemistry of CdS nanoparticles: a cor-
relation between optical and electrochemical band gaps. J Am Chem Soc
2001;123:8860e1.
[40] Misra A, Kumar P, Srivastava R, Dhawan SK, Kamalasanan MN, Chandra S.
Electrochemical and optical studies of conjugated polymers for three primary
colours. Indian J Pure Appl Phys 2005;43:921e5.
[41] Neto BAS, Lopes AS, Ebeling G, Gonçalves RS, Costa VEU, Quina FH, et al.
Photophysical and electrochemical properties of p-extended molecular 2,1,3-
benzothiadiazoles. Tetrahedron 2005;61:10975e82.
[42] Shafiee A, Salleh MM, Yahaya M. Determination of HOMO and LUMO of [6,6]-
phenyl C61-butyric pcid3-ethylthiophene ester and poly (3-octyl-thiophene-
2, 5-diyl) through voltammetry characterization. Sains Malays 2011;40:
173e6.
[43] Benati L, Montevecchi PC, Zanardi G. Thermal decomposition of 1,2,3-
benzothiadiazole. J Org Chem 1977;42:575e7.
[44] Lu S, Yang M, Luo J, Cao Y, Bai F. Novel alternating dioctyloxyphenylene
vinylene-benzothiadiazole copolymer: synthesis and photovoltaic perfor-
mance. Macromol Chem Phys 2005;206:664e71.
[45] Alsalme AM, Alghamdi AAB, Alhamdani AAGQ, Iraqi A. Synthesis and prop-
erties of alternating vinylene-benzothiadiazole-based copolymers with
carbazole and fluorene derivatives for photovoltaic applications. Int J Elec-
trochem Sci 2014;9:1920e41.
[46] Wen S, Pei J, Zhou Y, Li P, Xue L, Li Y, et al. Synthesis of 4,7-diphenyl-2,1,3-
benzothiadiazole-based copolymers and their photovoltaic applications.
Macromolecules 2009;42:4977e84.