Anthrathiadiazole Derivatives: Synthesis, Physical Properties and Two-photon Absorption

Article abstract of DOI:10.1002/chem.202100307

Anthrathiadiazole is a key synthon for the construction of large azaacenes, however, the attachment of different substituents onto the skeleton of anthrathiadiazole is difficult but highly desirable because it could be easy to enrich the structures of aza

Full text of DOI:10.1002/chem.202100307

Accepted Article
Accepted Article
Title: Anthrathiadiazole Derivatives: Synthesis, Physical Properties and
Two-photon Absorption
Authors: Qichun Zhang, Mingxuan Fan, Guangsheng Chen, Yu Xiang,
Junbo Li, Xianglin Yu, Wenying Zhang, Xueting Long, Liang
Xu, Jinjun Wu, and Ze Xu
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To be cited as: Chem. Eur. J. 10.1002/chem.202100307
Link to VoR: https://doi.org/10.1002/chem.202100307
01/2020

10.1002/chem.202100307
Chemistry - A European Journal
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Anthrathiadiazole Derivatives: Synthesis, Physical Properties and
Two-photon Absorption
Mingxuan Fan a, Guangsheng Chen a, Yu Xiang a, Junbo Li *a, Xianglin Yu c, Wenying Zhang b, Xueting
Long b, Liang Xu *b, Jinjun Wu a, Ze Xu c, Qichun Zhang *d
[a]
Mr, M. Fan, Mr. G. Chen, Mr Y. Xiang, Prof. J. Li, Mr. J. Wu
School of Chemistry and Environmental Engineering, Key Laboratory for Green Chemical Process of Ministry of Education
Wuhan Institute of Technology
Wuhan, China
E-mail: jbliwit@163.com
[b]
Ms W. Zhang, Ms X. Long, Dr. L. Xu
Department of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province
Shantou University
Shantou, China
E-mail: xuliang@stu.edu.cn
[c]
[d]
Prof. X. Yu, Mr. Z. Xu
School of Chemical Engineering and Pharmacy
Wuhan Institute of Technology
Wuhan, China
Prof. Q. Zhang
Department of Materials Science and Engineering
City University of Hongkong
E-mail: qiczhang@cityu.edu.hk
Supporting information for this article is given via a link at the end of the document.
Abstract: Anthrathiadiazole is a key synthon for the construction of
large azaacenes, however, the attachment of different substituents
onto the skeleton of anthrathiadiazole is difficult but highly desirable
because it could be easy to enrich the structures of azaacenes.
Here, we demonstrate that anthrathiadiazole derivatives with -Br, -
CN, and -OCH3 groups could be easily constructed through a
simple [4+2] cycloaddition reaction between a, a, a’, a’-tetrabromo
o-xylenes derivatives and benzo[c][1,2,5]thiadiazole-4,7-dione. The
structures of the as-prepared compounds with different substituents
were carefully characterized. Moreover, the basic physical
properties of the as-prepared anthrathiadiazole derivatives were
fully investigated, where the cyano-substituted derivative (BTH-CN)
has the highest stability and the methoxy-substituted derivative
(BTH-OCH3) is easy to be oxidized. Moreover, the two-photon
absorption (TPA) characteristics of different anthrathiadiazoles are
also studied by using the femtosecond Z-scan technique. The
results show that the fused anthrathiadiazole skeletons possess
large TPA cross-section values δ2 in the range of 3000-5000 GM,
where the nature, position and strength of the substituted groups
have strong effect on these values.
promising one is the replacement of sp2 C with hetero-atoms
(i.e. N, P, O) in the skeletons of acenes[6]. Specifically, N-
heterocycle-containing acenes (azaacenes) have been widely
investigated because of their adjustable charge-transporting
properties and excellent stability, which would have great
potential applications in organic optoelectrical devices[7]. More
recently, azaacenes have also been demonstrated to display
two-photon absorption (TPA)[8]. Such property would endow
them new applications in various fields including photodynamic
therapy[9], data storage[10], optical switching[11] and energy up-
conversion[12]. Thus, preparing new synthons to construct this
type of N-heteroacenes is highly desirable.
As one type of key synthons developed to approach diverse
azaacenes, anthrathiadiazole and their derivatives[13], have
been demonstrated to show promising charge transport
behaviors in organic electronics[14]
.
More importantly,
anthrathiadiazole derivatives can also be converted into stable
diamine intermediates through the reduction of lithium
aluminum hydride (LAH), which can be employed as powerful
“building blocks” to construct diverse azaacenes[15]. These
azaacenes might be good TPA candidates.
The traditional methods for the synthesis of anthrathiadiazole
are to use 2,3-dibromoanthracene-1,4-dione as the starting
materials, which firstly reacts with potassium phthalimide
through a nucleophilic substitution reaction, followed by the
hydrolysis with hydrazine to afford the intermediate
diaminoquinone. Then, this intermediate could react with thionyl
chloride in the refluxing condition to form the thiadiazole ring,
which could further react with different alkynyl lithium reagents
to produce anthrathiadiazole[13a]. One should note that the
report on the synthesis of the substituted anthrathiadiazoles is
rare. However, the substituted anthrathiadiazoles are very
important because they are not only key building units to enrich
Introduction
Acenes, consisting of linearly-fused benzene rings, have
been widely investigated as active elements in organic
electronics[1] such as organic light-emitting diodes (OLED)[2],
organic field-effect transistors (OFET)[3], organic photovoltaics
(OPVs)[4], etc. However, their synthesis, especially for
pentacene and higher acenes (n>5), is very difficult and tedious
since the increasing number of the fused benzene rings leads
to a dramatic decrease in their stability[5]. Thus, many methods
have been developed to address this issue, where the most
1
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10.1002/chem.202100307
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the structures of anthrathiadiazole-based materials but also
endow us the strong power to modulate their optical and
electronic properties. Such gap dramatically encourages us to
attach different substituted groups on the frameworks of
anthrathiadiazole and investigate their corresponding properties.
Herein, we use potassium iodide as a nucleophile to
eliminate the Br group on the a, a, a’, a’-tetrabromo-o-xylenes
derivative, followed by the [4+2] cycloaddition reaction with
benzo[c][1,2,5]thiadiazole-4,7-dione to produce four novel
CN, BTH-m-Br, BTH-o-Br, and BTH-OCH3 are located at 647
nm, 650 nm, 651 nm and 668 nm with shoulder peaks at 597
nm, 602 nm, 605 nm and 627 nm, respectively, which are
attributed to the intramolecular charge transfer (ICT). The
maximum absorption peaks of BTH-CN, BTH-m-Br, and BTH-
o-Br are similar to that of the reported parent compound BTH-C
(λmax = 656 nm)[18]. However, the maximum absorption peak of
BTH-OCH3 red-shifts nearly 12 nm, which may be caused by
the stronger ICT due to the electron-donating group (-OCH3).
As shown in Figure 1b, all compounds (BTH-CN, BTH-m-Br,
BTH-o-Br, BTH-OCH3) display different emission peaks at 684
nm, 700 nm, 701 nm and 739 nm, respectively. Compared with
BTH-m-Br, the emission wavelength of BTH-CN is blue-shifted
by 16 nm, while BTH-OCH3 is red-shifted by 39 nm, associating
with an obviously quenching fluorescence. Since there is a
strong ICT process in BTH-OCH3, when the electrons in BTH-
OCH3 are excited by light, the intersystem crossing happened,
which induces the quenching of the fluorescence. The
fluorescence quantum yields (Φ) of BTH-CN, BTH-m-Br, BTH-
o-Br, and BTH-OCH3 in CH2Cl2 are measured to be 0.044,
0.029, 0.022 and 0.005, respectively, with 9,10-
diphenylanthracene as the standard sample (Φ = 0.95 in
derivatives (BTH-m-Br, BTH-o-Br, BTH-CN and BTH-OCH3)[16]
Besides the effects of substituents on their normal
optoelectronic properties, the TPA property of the as-prepared
anthrathiadiazole-based materials are also studied. We find that
the nature, position and strength of the substituted groups on
the framework have strong effect on TPA δ2 values.
.
Compounds 1-6 and 8a-c are prepared according to the
reported procedure[17]. In order to obtain anthrathiadiazole
derivatives with different substitutes,
a
simple [4+2]
cycloaddition reaction with potassium iodide as the nucleophilic
reagent is used to construct four anthrathiadiazole derivatives
between a, a, a’, a’-tetrabromo o-xylenes derivatives and
benzo[c][1,2,5]thiadiazole-4,7-dione. Note that Br atom can also
act as the active site for the extension of π conjugate system,
which might provide a new strategy for the enrichment of
heteroacenes.
CH2Cl2)[19]
.
O
O
O
O
NO2
NO2
NH2
NH2
HNO3
Pd/C
H2
O
O
O
O
OH
O
O
N
N
N
N
N
N
AlCl3
pyridine
reflux
AgO
S
S
1
S
2
O
NH2
N
OH
C
SOCl2
4
5
6
3
O
N
N
O
O
TIPS
Br
S
N
N
Li
Br
Br
NBS, CCl4
reflux
O
S
Figure 1. UV-vis absorption (a) and Fluorescence spectra (b) of BTH-CN,
BTH-m-Br, BTH-o-Br, and BTH-OCH3 (10-5 M in CH2Cl2).
KI, NaH2PO2
R1
R1
R1
R2
9a
R2 Br
R2
R1 = CN, R2 = H
8a
7a
R1 = CN, R2 = H
R1 = CN, R2 = H
9b R1 = Br, R2 = H
9c R1 = H, R2 = Br
8b R1 = Br, R2 = H
8c R1 = H, R2 = Br
7b R1 = Br, R2 = H
7c R1 = H, R2 = Br
7d R1 = CH3O, R2 = H
9d R1 = CH3O, R2 = H
8d R1 = CH3O, R2 = H
The electrochemical properties of BTH-CN, BTH-m-Br, BTH-
o-Br, and BTH-OCH3 are measured by the cyclic voltametric
TIPS
TIPS
(CV)
analysis
in
CH2Cl2
solution
with
0.1
M
N
S
N
N
S
N
tetrabutylammonium hexafluorophosphate (Bu4NPF6) as the
supporting electrolyte. Ferrocene is used as an internal
standard. As shown in Figure 2, the CV curves of BTH-m-Br
and BTH-o-Br are very similar to each other, displaying two
reversible reduction waves and one reversible oxidation wave.
However, BTH-OCH3 shows one reversible reduction wave,
one reversible oxidation wave and one irreversible oxidation
wave, while BTH-CN exhibits two reversible reduction waves
and one reversible oxidation wave. The onset oxidative
potentials of BTH-CN, BTH-m-Br, BTH-o-Br, and BTH-OCH3
are measured to be 0.87 V, 0.72 V, 0.70 V, 0.50 V, respectively,
indicating that BTH-CN is the most difficult one to be oxidized
among all compounds due to the existence of the stronger
withdrawing group -CN. The HOMO energy levels of BTH-CN,
BTH-m-Br, BTH-o-Br and BTH-OCH3 are calculated to be -
5.67 eV, -5.52 eV, -5.50 eV, and -5.30 eV, respectively, through
the equation of EHOMO = -(Eonsetox + 4.80) eV.
Br
NC
TIPS
TIPS
BTH-CN
BTH-m-Br
TIPS
TIPS
N
N
N
S
N
S
H3CO
Br
TIPS
BTH- -Br
TIPS
o
BTH-OCH3
Scheme 1. Synthetic routes to the four anthrathiadiazole derivatives.
The UV–vis spectra of four compounds (BTH-CN, BTH-m-Br,
BTH-o-Br, BTH-OCH3) are recorded in CH2Cl2. All materials
show two sets of absorption peaks between 350-450 nm and
500-750 nm, where the maximum absorption peaks for BTH-
2
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Table 1. Optical and electrochemical data of BTH-CN, BTH-m-Br, BTH-o-Br and BTH-OCH3.
ox
red
Eonset
Eonset
LUMO
(eV)b
-3.89
-3.77
-3.74
-3.61
HOMO
(eV)c
-5.67
-5.52
-5.50
-5.30
Egap
(eV)d
1.78
1.75
1.76
1.69
Egap/λonset
(eV / nm)e
1.81/684
1.77/700
1.77/701
1.68/739
HOMO
(eV)f
-5.37
-5.15
-5.17
-4.93
LUMO
(eV)f
-3.5
-3.28
-3.28
-3.07
Egap
(eV)f
1.87
1.87
1.89
1.86
Comp
(V)a
0.87
0.72
0.70
0.50
(V)a
-0.91
-1.03
-1.06
-1.19
CN
m-Br
o-Br
OCH3
(a) The as-obtained values from cyclic voltammograms in CH2Cl2; (b) ELUMO = - (4.8 + Eonsetred); (c) EHOMO = - (4.8 + EonsetOx); (d) Egap
=
ELUMO - EHOMO; (e) Optical band gap, Egap = 1240/λonset; (f) The as-obtained values from theoretical calculations.
Figure 2. Cyclic voltammetry curves of BTH-CN, BTH-m-Br, BTH-o-Br and
BTH-OCH3 in CH2Cl2 solution containing 0.1 M TBAP electrolyte. Scanning
rate: 100 mV/s.
Figure 4. The open-aperture Z-scan results of BTH-CN, BTH-m-Br, BTH-o-
Br and BTH-OCH3.
The onset reductive potentials of BTH-CN, BTH-m-Br, BTH-o-
Br and BTH-OCH3 are measured to be -0.91 V, -1.03 V, -1.06 V,
-1.19 V, respectively, and the LUMO energy levels are
calculated to be -3.89 eV, -3.77 eV, -3.74 eV, -3.61 eV
red
respectively, through the equation of ELUMO =- (4.8 + Eonset
)
eV[20] . The change trends in HOMO and LUMO energy levels
and bandgaps of BTH-CN, BTH-m-Br, BTH-o-Br and BTH-
OCH3 are consistent with the results from the theoretical
calculations.
The molecular geometries of BTH-CN, BTH-m-Br, BTH-o-Br
and BTH-OCH3 are optimized by using density functional theory
(DFT) at the B3LYP/6-31G* level[21]. The ground state frontier
molecular orbitals of the optimized molecules are also calculated.
As shown in Figure 3, the HOMO orbitals of BTH-CN, BTH-m-
Br, BTH-o-Br and BTH-OCH3 are similar to each other, and the
LUMO orbitals of BTH-CN, BTH-m-Br, BTH-o-Br and BTH-
OCH3 are also similar. All HOMOs are mainly delocalized on
anthracene unit, thiadiazole ring except sulfur atom and alkyne
groups, while all LUMOs are mainly localized on anthracene unit,
thiadiazole ring including sulfur atom and alkyne groups,
respectively. Note that the calculated HOMO energy levels are
close to the results from CV experiment, which have been
summarized in Table 1.
Actually, there are two main methods including two-photon
excited fluorescence (TPEF) and Z-scan techniques for the
measuring of TPA cross sections. The TPEF method is based
on a TPA-induced fluorescence intensity measurement, where
this method requires the fluorescent sample, limiting its
application on some nonfluorescent systems. For the Z-scan
method, the sample is moved along the path of a focused laser
beam, and the light intensity as a function of its position along
Figure 3. Wave functions for the HOMO and LUMO of BTH-CN, BTH-m-Br,
BTH-o-Br and BTH-OCH3.
3
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the z-axis is recorded. The limitation of this method is that other
effects such as thermal lens effect may contribute to the 2PA
cross-sections.[22] The two-photon absorption properties of BTH-
CN, BTH-m-Br, BTH-o-Br and BTH-OCH3 are characterized by
an open-aperture femtosecond Z-scan technique. The excitation
source is a Ti:sapphire oscillator seeded regenerative amplifier
(pulse energy of 1.3 mJ at 800 nm) with an adjustable excitation
intensity. The as-obtained Z-scan curves (Figure 4) indicate that
BTH-CN, BTH-m-Br, BTH-o-Br and BTH-OCH3 have TPA
properties with the cross-section values (δ2) of 3167 GM, 3461
GM, 3179 GM and 4913 GM, respectively. Our results clearly
indicate that the value of the TPA cross sections (δ2) strongly
depends on the nature, position, and strength of the substituted
groups on the same frameworks. Since Br atom is a weaker
electron-withdrawing group than cyano species, the TPA cross
sections (δ2) of BTH-m-Br (3461) and BTH-o-Br （3179）are
larger than that of BTH-CN (3167). Comparing to the Br position,
the δ2 of m-substituted BTH is much larger than the o-substituted
one. As to the electron-donating group methoxyl, the two-photon
absorption cross section value is the strongest one. Our results
clearly confirm that the electron-rich group on the electron-
deficient frameworks normally produces the larger TPA cross-
sections δ2. Moreover, some recently reported acene and
nanographene-based TPA materials were listed in table S1.
Keywords: azaacene • anthrathiadiazole • synthon • two-photon
absorption • cycloaddition
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Comp
δ2max/GM
3461
3179
4913
3167
BTH-m-Br
BTH-o-Br
BTH-OCH3
BTH-CN
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compounds not only exhibited a potential nonlinear optical
application, but also could have a great potential to enrich the
number of azaacenes. We also found that the TPA cross-
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Acknowledgements
This work was supported by National Science Foundation of
China (No. 51203127, 20901063, 52073167 and 21702132),
Guangdong Basic and Applied Basic Research Foundation.
National Training Program of Innovation and Entrepreneurship
for Undergraduates (201810490019). QZ thanks the support
from starting funds from City University of Hongkong.
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Entry for the Table of Contents
Here, by using
a simple [4+2] cycloaddition reaction between a, a, a’, a’-tetrabromo o-xylenes derivatives and
benzo[c][1,2,5]thiadiazole-4,7-dione, the substituted anthrathiadiazoles with -Br, -CN, and -OCH3 groups could be easily constructed.
The as-obtained compounds display the two-photon absorption, where their cross-section values are strongly affected by the nature,
position and strength of the substituted groups.
6
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