Coplanar bithiazole-centered heterocyclic aromatic fluorescent compounds having different donor/acceptor terminal groups

Article abstract of DOI:10.1021/jo302706t

A family of stable and soluble bithiazole-centered heterocyclic aromatic fluorescent compounds is described herein. All these multiple N-donor containing compounds have effective π-conjugated systems and different imidazole, pyridine, thiophene, triphenyl

Full text of DOI:10.1021/jo302706t

Article
pubs.acs.org/joc
Coplanar Bithiazole-Centered Heterocyclic Aromatic Fluorescent
Compounds Having Different Donor/Acceptor Terminal Groups
Tao Tao, Yu-Xin Peng, Wei Huang,* and Xiao-Zeng You
State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and
Chemical Engineering, Nanjing University, Nanjing 210093, P. R. China
S
* Supporting Information
ABSTRACT: A family of stable and soluble bithiazole-centered heterocyclic
aromatic fluorescent compounds is described herein. All these multiple N-
donor containing compounds have effective π-conjugated systems and different
imidazole, pyridine, thiophene, triphenylamino, benzoic acid, and ethyl
benzoate tails showing distinguishable D−A−A−D and A−A−A−A structures.
X-ray single-crystal structures of seven compounds indicate that all of the
bithiazole cores have the same trans coplanar configuration but exhibit different
dihedral angles with their adjacent aromatic heterocycles (4.5(6)−69.7(3)°).
Optical and electrochemical results demonstrate that the TPA-terminated
bithiazole compound 2TPA2TZ has yellow fluorescence and reversible redox
activity as well as extraordinarily high thermal stability. Theoretical and
experimental studies have been made to reveal the differences from related
compounds with adjustable electronic properties. The internal reorganization
energy (λ) studies have been carried out to indicate the differences between the bithiazole-based derivatives and the
corresponding bithiophene-based counterparts.
the most powerful tools to characterize the molecular geometry
and packing for organic small molecules.9
INTRODUCTION
■
In recent years, linear π-conjugated semiconducting com-
pounds have been extensively studied in the field of molecular-
based materials1 such as organic and polymeric light emitting
diodes,2 field effect transistors,3 and photovoltaic cells.4
Compared with the corresponding polydisperse polymers, the
monodisperse oligomers are excellent model compounds and
have many advantages including their well-defined chemical
structures, better solubility, easier purification, fewer defects,
greater synthetic reproducibility, and the possibility of
introducing versatile functionalities.5 However, all these present
both opportunities and challenges to rational design and
synthesis of extended heterocyclic aromatic systems for
constructing high-performance electronic materials.
Thiophene-/thiazole-containing conjugated oligomers repre-
sent an intriguing and promising class of materials because they
are believed to be ideal functional elements and building blocks
in the studies of molecular electronics.6 More importantly, the
enormous and attractive potential of structural variations makes
possible the fine-tuning of optoelectronic properties in a wide
range.7 However, the device applicability of such materials can
be influenced by various factors, including narrow energy gap,
appropriate highest occupied molecular orbital (HOMO) and
lowest unoccupied molecular orbital (LUMO) energy levels,
high thermal durability, ease for the mobility of hole and
electron, and the geometrical packing in the solid state.8 Thus,
X-ray single-crystal diffraction, which is believed to be a bridge
between theory and experiment, has been proved to be one of
In our previous work, a series of 1,10-phenanthroline-based
and oligothiophene-based heterocyclic aromatic compounds
with terminal thienyl, imidazolyl, and pyridyl groups has been
described.10 Furthermore, temperature-dependent semicon-
ducting and photoresponsive properties of self-assembled
nanocomposite films and nanodevices fabricated from these
compounds and their metal complexes have been explored.11 In
view of relatively fewer investigations on the thiazole-based
semiconducting heterocyclic aromatic derivatives in comparison
with the thiophene-based ones, we have extended our work
herein on the bithiazole-centered semiconducting and
fluorescent compounds with the same coplanar core and two
chelating nitrogen atoms as the coordination sites, bearing
various electron-donating and electron-withdrawing tails,
namely bromo, imidazolyl, pyridyl, thienyl, triphenylamino,
benzoic acid, and ethyl benzoate groups (Scheme 1). Two n-
butyl chains are introduced herein on the β-position of each
bithiazole unit in order to (a) increase the solubility in
conventional organic solvents but minimize the effect on the
increase of molecular planarity, (b) facilitate the related C−C
bond and C−N bond cross-coupling reactions and improve the
final yields, (c) enhance the weak donor property of the
thiazole ring.
Received: December 13, 2012
© XXXX American Chemical Society
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Scheme 1. Synthetic Route of Bithiazole-Based Heterocyclic Aromatic Fluorescent Compounds
The aim of incorporating various donor and acceptor
substituents into one molecule is to finely tune their electronic
structures and compare their spectroscopic, electrochemical,
and thermal properties. The acquirement of these linear
heterocyclic aromatic compounds especially the single-crystal
structures prompts us to further explore the possible rules
between their structures and properties, for example, the
relationship between the number of aromatic heterocycles and
the electronic and fluorescence spectra, energy gap alterations,
the limitation of solubility of compounds which is also
influenced by the substituent effects. In addition, theoretical
and experimental studies have been carried out to reveal the
differences between the bithiazole-based derivatives and the
corresponding bithiophene-based counterparts.
In comparison with bithiazole bearing no substituent, our
results demonstrate that the introduction of two n-butyl chains
on the β-position of each thiazole ring can effectively increase
the solubility in conventional organic solvents but minimize the
effect on the increase of molecular planarity, facilitate the
related C−C bond and C−N bond cross-coupling reactions,
improve the final yields, and enhance the weak donor property
of the thiazole ring. As a result, the benzoic acid extended
bithiazole compound 2BA2TZ can be successfully prepared by
the Suzuki−Miyaura reaction in a high yield of 89%. However,
the solubility of this compound is still not good enough in
chloroform. To solve this problem and keep its electronic
structure, compound 2EB2TZ was synthesized by the conven-
tional ethyl esterification in a yield of 68%. It is worth
mentioning that 2EB2TZ has been further confirmed by the
1
1H−1H and H−13C correlation spectroscopy (COSY) NMR
RESULTS AND DISCUSSION
■
shown in Figures SI9c and SI9d (Supporting Information). As
anticipated, triphenylamino- and pyridyl-terminated com-
pounds 2TPA2TZ and 2Py2TZ were synthesized with
satisfactory yields in the presence of [Pd(PPh3)4] catalyst by
using a strong cross-coupling reagent, i.e. 4-(diphenylamino)-
phenylboronic acid and 4-pyridinylboronic acid. As shown in
Scheme 1, thiophene-terminated bithiazole compound 2T2TZ
was also first prepared by the classical C−C bond cross-
coupling reaction by the treatment of Grignard reagents
obtained from corresponding bithiazole-based bromides and
magnesium turnings in the presence of [NiCl2(dppp)] catalyst
in dry THF in a yield of 53%.
Syntheses and Spectral Characterizations. Our syn-
thetic strategy was based on the routes shown in Scheme 1, in
which the starting material 5,5′-dibromo-4,4′-dibutyl-2,2′-
bithiazole (2Br2TZ) was prepared according to the previously
reported approaches.12 All the target compounds were prepared
by carbon−carbon (C−C) bond or carbon−nitrogen (C−N)
bond cross-coupling reactions. The use of different cross-
coupling methods, such as Kumada−Corriu, Suzuki−Miyaura,
and Ullmann reactions, have been carried out to optimize the
experimental conditions in order to prepare the linear π-
conjugated compounds with high yields. As shown in Figures
SI1−9 (Supporting Information), all the heterocyclic aromatic
As illustrated in Figure 1, all new compounds show
characteristic absorptions at 332−408 nm in their electronic
spectra corresponding to the π−π* transitions between
adjacent aromatic heterocycles. The strong absorption peak at
1
compounds have been characterized by H, 13C NMR and EI-
TOF-MS spectra, and the results clearly demonstrate the
formation of the expected compounds.
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emission spectra. However, the molar extinction coefficient of
2BA2TZ (ε = 13900 L·mol−1·cm−1) is less than that of
2EB2TZ (ε = 37600 L·mol−1·cm−1) as depicted in Figure 1a
and Table 1. Compared with the oligothiophene-based
aromatic heterocyclic compounds10d showing characteristic
fluorescence emissions, red-shifts are observed for these
bithiazole-based counterparts to different extents especially
for the pyridyl-, thienyl-, and triphenylamino-terminated
bithiazole compounds.
Single-Crystal and Molecular Packing Structures. In
this work, we tried to obtain as many single-crystal structures of
our compounds as possible in order to fully characterize their
molecular geometry and further illuminate and compare their
packing modes and supramolecular interactions. As a result,
single-crystal structures of seven compounds, i.e., 2TZ,
2Br2TZ, 2Im2TZ, 2Py2TZ, 2T2TZ, 2BA2TZ, and 2EB2TZ
(Tables 2 and SI1, Supporting Inforamtion), have been
obtained. It is interesting to mention that the central two
thiazole rings of all the compounds are found to adopt the same
coplanar and trans configuration. However, the coplanar
bithiazole cores display different dihedral angles with their
adjacent aromatic heterocycles to reduce the steric hindrance as
depicted in Figure 2.
On the one hand, they all have many N-donors in their
molecular structures such as bithiazole, imidazole and pyridine
units. On the other hand, compounds 2Im2TZ and 2Py2TZ
have the alternate A−A−A−A heterocyclic aromatic system,
while compound 2T2TZ shows a distinguishable D−A−A−D
structure. On the basis of the two aforementioned aspects, it is
possible for us to finely tune their optoelectronic properties by
introducing a variety of metal ions by means of the formation of
coordinative bonds.
The molecular lengths of linear compounds 2Im2TZ,
2Py2TZ, 2T2TZ, 2BA2TZ, and 2EB2TZ are longer than
1.33 nm. It is noted that these molecules show good planarity
except compound 2Im2TZ. The stereochemistry and con-
formation of 2Im2TZ may be interesting in forming the
hydrogen-bonding contacts and coordinative bonds because of
the free rotation of the C−N single bonds between the two side
imidazole rings and the central bithiazole plane.10c The crystal
structure of 2Im2TZ herein displays the trans/trans/trans
conformation and the two side imidazole rings are not coplanar
to the central bithiazole unit with the same dihedral angle as
large as 69.7(3)°. It is believed that the increase of
intramolecular planarity, which could reduce the reorganization
energy and enhance the electronic coupling between adjacent
molecules, would be much more efficient for the transportation
of charge carriers.13 For this reason, it is predicted that 2Im2TZ
has larger reorganization energy than others due to its large
dihedral angles between the thiazole and the imidazole rings in
the solid state, and this turns out to be true from the following
reorganization energy calculations for this family of com-
pounds.
The crystal-packing view of this family of linear heterocyclic
aromatic compounds is also shown in Figure 3 and Figure SI10
(Supporting Information), where the intermolecular hydrogen
bonding and π−π stacking interactions are found. It is worth
mentioning that the packing structure of 2T2TZ has the
multiple S···S short contacts (3.380(10) and 3.557(16) Å) and
strong π−π stacking interactions between neighboring thiazole/
thiazole and thiazole/thiophene rings with the centroid-to-
centroid separations of 3.763(3) and 3.776(7) Å, respectively.
Figure 1. UV−vis absorption spectra (a), fluorescence emission
excited at 350 nm (b), and their visual photographs (c) for the
heterocyclic aromatic compounds in their methanol solutions at room
temperature with the same concentration of 5.0 × 10−5 mol·L−1.
high-energy band (302 nm) for 2TPA2TZ is assigned as the
interring electronic transitions among the three phenyl rings of
TPA. Moreover, this family of linear heterocyclic aromatic
compounds is fluorescent active. In particular, compound
2TPA2TZ shows an extraordinarily strong fluorescence peak at
554 nm with the luminescence quantum yield (Φ) of 22% by
using anthracene as a standard (Φstd = 27%, see the Supporting
Information). At the same time, it exhibits a strong UV−vis
absorption peak at 408 nm (ε = 36700 L·mol−1·cm−1). In
comparison with compound 2TZ, similar bathochromic shifts
have been found in the fluorescence emission spectra of
compounds 2Im2TZ, 2Py2TZ, and 2T2TZ when the number
of aromatic heterocycles (namely delocalized π-systems) is
increased. In addition, compounds 2BA2TZ and 2EB2TZ
show similar λmax in the UV−vis absorption and fluorescence
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Table 1. UV-Vis Absorption and Fluorescence Emission Data, Optical, Electrochemistry, Calculated HOMO−LUMO Energy
Gaps (Eg), and Internal Reorganization Energy (λ) for Related Heterocyclic Aromatic Compounds
a
b
c
d
e
f
g
h
UV−vis λmax
ε
Egopt
Egcalcd
fluorescence λmax
Td10
Eox
EHOMO
(eV)
ELUMO
(eV)
λ2TZ
λ2T
onset
compd
2TZ
[nm (eV)]
(L·mol−1·cm−1
)
(eV)
(eV)
(nm)
(°C)
(V)
(eV)
(eV)
332 (3.73)
338 (3.67)
352 (3.52)
365 (3.40)
393 (3.16)
408 (3.04)
370 (3.35)
370 (3.35)
25000
26300
42200
47700
48300
36700
13900
37600
3.42
3.32
3.22
3.04
2.74
2.60
2.97
2.96
4.16
3.88
3.84
3.59
3.05
3.07
3.46
3.46
389
413
414
447
494
554
458
171
205
238
299
258
437
268
296
0.68
1.06
0.94
0.61
0.62
0.35
0.95
0.82
−5.78
−6.16
−6.04
−5.71
−5.72
−5.45
−6.05
−5.92
−2.36
−2.84
−2.82
−2.67
−2.98
−2.85
−3.08
−2.96
0.39
0.39
0.78
0.34
0.31
0.40
0.36
0.37
0.36
0.35
0.73
0.27
0.29
0.34
0.30
0.30
2Br2TZ
2Im2TZ
2Py2TZ
2T2TZ
2TPA2TZ
2BA2TZ
2EB2TZ
463
a
b
Optical energy gap determined from the UV−vis absorptions in solution. The geometries are calculated by the B3LYP method and 6-31G* basis
c
d
e
set. 10% weight loss temperature. Oxidation onset potentials determined from DPV vs Fc/Fc+. Calculated from EHOMO = −(Eox
+ 5.10).
onset
f
g
h
Calculated from ELUMO = EHOMO + Egopt. Calculated the internal reorganization energy for bithiazole-based model compounds. Calculated the
internal reorganization energy for bithiophene-based compounds.
Table 2. Crystal Data and Structure Refinements for Seven Compounds: 2TZ, 2Br2TZ, 2Im2TZ, 2Py2TZ, 2T2TZ, 2BA2TZ,
and 2EB2TZ
compd
formula
2TZ
2Br2TZ
2Im2TZ
2Py2TZ
2T2TZ
2BA2TZ·(DMF)2
2EB2TZ
C14H20N2S2
280.46
C14H18Br2N2S2
438.24
C20H24N6S2
412.59
C24H26N4S2
434.63
C22H24N2S4
444.71
C28H28N2O4S2·(C3H7NO)2 C32H36N2O4S2
666.86
formula wt
T (K)
576.77
291(2)
0.71073
291(2)
291(2)
291(2)
291(2)
291(2)
291(2)
wavelength/Å
cryst size (mm)
0.71073
0.71073
0.71073
0.71073
0.71073
0.71073
0.12 × 0.12 ×
0.14
0.10 × 0.12 ×
0.12
0.10 × 0.12 ×
0.12
0.10 × 0.11 ×
0.12
0.10 × 0.11 ×
0.11
0.10 × 0.13 × 0.15
0.10 × 0.11 ×
0.11
cryst syst
space group
a (Å)
monoclinic
P21/c
triclinic
monoclinic
P21/c
triclinic
monoclinic
P21/c
triclinic
triclinic
P1
̅
P1
̅
P1
̅
P1
̅
8.103(2)
9.953(3)
10.356(4)
90
5.142(1)
8.5329(17)
9.860(2)
84.688(3)
83.755(2)
85.838(3)
427.35(15)
1/1.703
13.393(2)
8.3690(14)
10.1189(16)
90
5.4824(15)
9.311(3)
11.760(3)
82.339(4)
77.410(3)
73.259(4)
559.4(3)
1/1.290
5.175(13)
25.53(6)
9.45(2)
90
5.4606(19)
12.111(4)
14.081(5)
100.073(5)
96.591(7)
101.281(6)
888.4(5)
1/1.247
8.436(6)
9.551(7)
10.274(7)
102.203(9)
105.772(9)
100.009(9)
754.7(9)
1/1.269
b (Å)
c (Å)
α (deg)
β (deg)
γ (deg)
V (Å3)
Z/Dcalcd (g/cm3)
116.195(4)
90
107.022(2)
90
117.87(4)
90
749.4(4)
2/1.243
300
1084.5(3)
2/1.263
436
1104(4)
2/1.338
468
F(000)
218
230
354
306
μ (mm−1
)
0.341
4.978
0.263
0.256
0.441
0.198
0.215
max/min
transmission
0.9603/0.9538
0.6359/0.5865
0.9742/0.9691
0.9748/0.9699
0.9572/0.9531
0.9805/0.9710
0.9788/0.9767
hmin/hmax
−8/9
−6/6
−15/14
−6/6
−6/6
−6/4
−10/7
k
min/kmax
min/lmax
data/param
−11/10
−12/10
1317/83
−10/7
−11/11
1467/93
−7/9
−12/12
−11/10
−12/13
−30/19
−11/11
−13/14
−16/16
−11/11
−10/12
l
1896/128
R1 = 0.0385
wR2 = 0.1104
R1 = 0.0486
wR2 = 0.1174
1.10
1931/137
R1 = 0.0454
wR2 = 0.1174
R1 = 0.0596
wR2 = 0.1270
0.97
1932/184
R1 = 0.0918
wR2 = 0.2119
R1 = 0.1891
wR2 = 0.2475
0.95
2850/222
R1 = 0.0908
wR2 = 0.2409
R1 = 0.1748
wR2 = 0.2773
1.05
2623/184
R1 = 0.0354
wR2 = 0.0763
R1 = 0.0528
wR2 = 0.0823
0.92
final R indices [I > R1 = 0.0486
R1 = 0.0535
wR2 = 0.1319
R1 = 0.0574
wR2 = 0.1344
1.05
a
2o(I)
wR2 = 0.1337
R indices (all
R1 = 0.0519
wR2 = 0.1386
1.06
a
data
S
max/min Δρ
0.51/−0.38
1.10/−1.17
0.21/−0.22
0.22/−0.43
0.28/−0.30
0.31/−0.37
0.15/−0.16
(e·Å−3
)
a
2
2
R1 = Σ||Fo| − |Fc||/Σ|Fo|, wR2 = [Σ[w(Fo − Fc2)2]/Σw(Fo )2]1/2
.
Thermal Stability. Thermal durability of π-conjugated
unchangeable when the temperature is below 200 °C and the
Td10 values for them are found to range from 205 to 437 °C.
Furthermore, the bithiazole derivatives 2Py2TZ, 2EB2TZ, and
2TPA2TZ show higher performance in the thermal stability
compared with other bithiazole-based compounds. In partic-
ular, the Td10 value for the TPA-extended bithiazole compound
2TPA2TZ is 437 °C, indicative of excellent thermal stability.
Electrochemical Properties. It is generally believed that
the HOMO of the D−A oligomer is determined by the HOMO
of the donor unit, while the LUMO of D−A oligomer is
small molecules has significant impact on the device perform-
ance, which is one of the most essential parameters for the fine-
tuned optoelectronic applicability.14 In this work, eight
bithiazole-based aromatic heterocyclic compounds have been
checked by the TGA measurements, and a parameter of Td10
(10% weight-loss temperature) is used to describe the thermal
stability of these compounds. As shown in Figure 4, the TGA
curves of 2Br2TZ, 2Im2TZ, 2Py2TZ, 2T2TZ, 2TPA2TZ,
2BA2TZ, and 2EB2TZ indicate that they can remain
D
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Figure 2. ORTEP diagrams (30% thermal probability ellipsoids) of the molecular structures of 2TZ, 2Br2TZ, 2Im2TZ, 2Py2TZ, 2T2TZ, 2BA2TZ,
and 2EB2TZ showing the dihedral angles and relative configurations between adjacent aromatic heterocycles.
controlled by the LUMO of acceptor unit.15 Therefore, the
electrochemical behavior of bithiazole-based heterocyclic
aromatic compounds was examined by the cyclic voltammetry
(CV) and the differential pulse voltammetry (DPV) measure-
ments in their 1.0 × 10−3 mol·L−1 CH2Cl2 solutions containing
0.1 mol·L−1 TBAClO4 as the supporting electrolyte at different
scan rates (10, 20, 50, and 100 mV·s−1). All potentials reported
herein were calibrated with the ferrocene/ferrocenium couple
(Fc/Fc+) as internal standard. Oxidation onset potentials
(Eoxonset) as well as HOMO/LUMO energy levels were
determined by the DPV and absorption data, which are
summarized in Table 1. The onset oxidation was measured
relative to the Fc/Fc+ couple where an energy level of −5.10 eV
versus vacuum was assumed.16
As depicted in Figures 5a, compound 2TPA2TZ shows
reversible and well-defined redox response in the CV
measurements. However, the other bithiazole derivatives do
not present good enough electrochemical activity in the CV
experiments, which are consistent with previously reported17
bithiazole oligomers. Consequently, the DPV method is used to
further explore the electrochemical properties for related
compounds in this case. As can be seen in Figure 5b, one or
two oxidation waves have been observed for all compounds,
and the oxidation potentials and the measured currents are
found to be dependent on their molecular structures. The first
oxidation wave can be attributed to the formation of cation-
radical species and the second one is ascribed to the successive
oxidation of cation-radical to its corresponding dication, which
have been observed previously in other thiophene and thiazole
compounds.17,18 In particular, compound 2T2TZ displays three
oxidation waves in the range 0.7−1.2 V, indicative of the
existence of three stable cation-radical species, which are
suggested to be the first and the second oxidation states of
thiophene18b (0.75 and 1.08 V) and the first oxidation state of
thiazole17c (0.93 V). The Eox
of these π-functionalized
onset
bithiazole compounds were determined to be 0.94 V for
2Im2TZ, 0.61 V for 2Py2TZ, 0.62 V for 2T2TZ, and 0.35 V
for 2TPA2T, respectively.
Density Function Theory (DFT) Computations. DFT
calculations were carried out with the Gaussian09, Revision
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C.01 programs19 using the B3LYP method and 6-31G* basis
set. The fixed atom coordinates of eight bithiazole-based
compounds, which are based on the structural parameters
determined by the X-ray diffraction method and full
optimization, are used for the HOMO and LUMO gap
calculations (Table 1).
The resultant HOMO−LUMO gaps for bithiazole-incorpo-
rated heterocyclic aromatic compounds 2Im2TZ, 2Py2TZ,
2T2TZ, and 2TPA2TZ are 3.84, 3.59, 3.05, and 3.07 eV,
respectively, which are analogous to their UV−vis absorption
peaks. In addition, the DFT and UV−vis absorption experi-
ments show that compounds 2BA2TZ and 2EB2TZ have
similar electronic structures. That is to say, the introduction of
two ethyl groups on each benzoic acid unit is significant in
increasing the solubility in chloroform without impacting the
electronic structure.
According to the DPV measurements, further analyses of the
frontier orbitals reveal that the introduction of electron-
donating groups raises the HOMO energy levels, while the
introduction of electron-withdrawing groups lowers the LUMO
energy levels, which will greatly decrease the HOMO−LUMO
gaps of resultant compounds (see Figure SI12, Supporting
Information). It is noted that there is a nearly linear
relationship between the experimentally determined energy
levels (DPV and UV−vis absorption spectra) and the
theoretically calculated ones for the HOMOs and LUMOs of
these thiazole/thiophene/imidazole/pyridine heterocyclic ar-
omatic hybrids (Figure 6). This relationship demonstrates that,
despite the uncertainty in the calculated absolute values,
theoretical calculations can act as a very useful tool to predict
and guide the synthesis of future bithiazole oligomer materials.
To make further comparisons from a theoretical and
experimental perspective, investigations on the internal
reorganization energy (λ) have been done at the B3LYP/6-
31G* level for a series of π-conjugated bithiazole-based
derivatives and the corresponding bithiophene-based counter-
parts.20 Compared with inorganic semiconductors, the charge
mobility of organic semiconducting materials is generally
determined by a hopping transport process at room temper-
ature.13b According to Marcus theory (eq 1),21 self-exchange
rate and the charge mobility are determined by the electronic
coupling between adjacent molecules (t) which needs to be
Figure 3. Perspective view of the packing structure in compound
2T2TZ showing the S···S short contacts and strong π−π stacking
interactions.
Figure 4. Thermograms of bithiazole-based compounds 2TZ,
2Br2TZ, 2Im2TZ, 2Py2TZ, 2T2TZ, 2TPA2T, 2BA2TZ, and
2EB2TZ.
Figure 5. CV (a) and DPV (b) for related heterocyclic aromatic compounds in CH2Cl2 (1.0 × 10−3 mol·L−1) containing 0.10 mol·L−1 of TBAClO4
under argon. In (a), different scanning rates of 10, 20, 50, and 100 mV/s are used for 2TPA2TZ vs Fc/Fc+.
F
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Figure 6. HOMOs and LUMOs of 2TZ (a), 2Br2TZ (b), 2Im2TZ (c), 2Py2TZ (d), 2T2TZ (e), 2TPA2T (f), 2BA2TZ (g), and 2EB2TZ (h)
calculated with B3LYP/6-31G*. (i) Energy level correlation between the DPV, UV−vis absorption spectra, and the computational data.
maximized, and the reorganization energy (λ) which needs to
be small for efficient charge transport22
CONCLUSION
■
In summary, synthetic, structural, thermal, computational, and
spectral comparisons have been carried out for a series of
imidazole/pyridine/thiophene/benzene/triphenylamino-con-
taining heterocyclic aromatic fluorescent compounds with the
same coplanar bithiazole centers and high stability and
solubility. The differences between cross-coupling approaches
and experimental conditions on the C−C bond and C−N bond
formation, molecular conformation and dihedral angles
between neighboring heterocycles, energy gaps and energy
levels, and electronic, fluorescent, and electrochemistry spectra
have been systematically investigated. X-ray single-crystal
structures for this family of multiple N-donor containing
compounds reveal the same trans and coplanar configuration in
the bithiazole core with two n-butyl chains on each β position
but distinguishable dihedral angles between adjacent aromatic
heterocycles. Optical and electrochemical results indicate that
the TPA-terminated bithiazole compound 2TPA2TZ has a
yellow fluorescent and electrochemical activity. Meanwhile,
2Py2TZ, 2EB2TZ and 2TPA2TZ show excellent performance
in the thermal stability. Overall, they may be good candidate
molecules toward device fabrication. It is also noted that
introducing the two ethyl chains on benzoic acid from 2BA2TZ
to 2EB2TZ is significant in increasing the solubility, thermal
durability and molar extinction coefficient without impacting
the electronic structure.
kct = 4πt2/h(1/4πλkbT)1/2exp(−λ/4kbT)
(1)
where kb is the Boltzmann constant, h is the Planck constant,
and T is the temperature. The reorganization energy (λ)
depicts the changes in the geometry of two molecules during
the electron transfer reaction.22 It has two contributions, i.e., an
internal one and an external one. The contribution of the
environmental factor (intermolecular) to the reorganization
energy is expected to be small in organic solids and hence only
the intramolecular reorganization energy is calculated.13b In this
paper, the bithiazole derivatives exhibit slightly larger internal
reorganization energy than the bithiophene units. As shown in
Table 1, fortunately, these λ values may not seem enormous,
which are consistent with those previously reported oligothio-
phenes23 (λ = 0.26 eV for α-sexithiophene, λ = 0.29 eV for α-
tetrathiophene, and λ = 0.36 eV for α-bithiophene).
Comparatively speaking, compounds 2Im2T and 2Im2TZ
have larger λ values which can be explained commendably by
the presence of big dihedral angles between the thiazole/
thiophene and the imidazole rings in their crystal structures.
Nevertheless, compounds 2Py2T and 2T2TZ are predicted to
be good candidates for investigations on the design and
synthesis of π-conjugated oligomers for OFET materials from a
theoretical and experimental perspective.
Our theoretical studies are in good agreement with the
corresponding photophysical and electrochemical studies. The
G
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evaporation in air at room temperature for 3 days. Mp: 70−72 °C.
Main FT-IR absorptions (KBr pellets, cm−1): 3398 (b), 2950 (s), 2921
(s), 2858 (s), 1639 (w), 1498 (s), 1444 (s), 1401 (s), 1366 (m), 1093
internal reorganization energy (λ) for these compounds has
been calculated using the B3LYP method and 6-31G* basis set
to study their electronic structures and compare the differences
between the bithiazole and bithiophene counterparts. This
finding highlights the fact that these bithiazole derivatives
exhibit slightly larger internal reorganization energy than the
corresponding bithiophene units and the variation reorganiza-
tion behavior is explained commendably by using the molecular
planarity and crystal packing model. Further studies are being
undertaken on the field-effect, light-emitting, photoresponsive
and photovoltaic properties of these linear multiple N-donor
containing aromatic heterocycle-based nanowires, nanocompo-
site films, and nanodevices in our laboratory.
1
(m), 1025 (s), 1006 (s), 957 (m), 865 (m), 660 (m). H NMR (500
MHz, CDCl3) δ: 2.75 (t, 4H, butyl), 1.68 (m, 4H, butyl), 1.35 (m, 4H,
butyl), 0.95 (t, 6H, butyl). 13C NMR (125 MHz, CDCl3) δ: 160.8,
159.0, 114.6, 31.3, 31.2, 22.3, 13.8. EI-TOF-MS (m/z): calcd for
[C14H18Br2N2S2]+ 438.2, found 437.8. Anal. Calcd for C14H18Br2N2S2:
C, 38.37; H, 4.14; N, 6.39. Found: C, 38.52; H, 4.41; N, 6.18.
2Im2TZ: A solution containing compound 2Br2TZ (0.83 g, 1.90
mmol), imidazole (5.20 g, 76.38 mmol), Cs2CO3 (3.68 g, 11.29
mmol), and anhydrous CuSO4 (16 mg, 0.10 mmol) in DMF (30 mL)
was heated to 140 °C for 72 h under argon atmosphere. The reaction
mixture was then cooled to room temperature and the solid was
removed by filtration and rinsed thoroughly with CHCl3 until no more
products could be detected by TLC. The filtrate was concentrated
using a rotary evaporator to give brown oil, and the residue was
dissolved in CHCl3 (200 mL) and washed thoroughly by brine to
remove excess imidazole which could be detected by TLC (iodine
fuming). The organic layer was dried by anhydrous MgSO4 and
filtered. The organic solvent was removed at reduced pressure. The
desired compound 2Im2TZ was finally separated by silica gel column
chromatography using chloroform as an eluent affording yellow solid
in a yield of 0.43 g (55%). The yellow single crystals of 2Im2TZ
suitable for X-ray diffraction measurement were obtained from ethyl
acetate (EA) by slow evaporation in air at room temperature for 3
days. Mp: 187−189 °C. Main FT-IR absorptions (KBr pellets, cm−1):
3409 (b), 3097 (m), 2907 (m), 1552 (vs), 1475 (m), 1407 (m), 1049
(m), 771 (m), 653 (m). 1H NMR (500 MHz, CDCl3): δ 7.67 (s, 2H,
imidazole), 7.25 (s, 2H, imidazole), 7.12 (s, 2H, imidazole), 2.62 (t,
4H, n-butyl), 1.66 (m, 4H, n-butyl), 1.30 (m, 4H, n-butyl), 0.89 (t, 6H,
n-butyl). 13C NMR (125 MHz, CDCl3): δ 157.4, 153.2, 138.7, 130.6,
129.6, 121.8, 31.2, 28.1, 22.3, 13.7. EI-TOF-MS (m/z): calcd for
[C20H24N6S2]+ 412.6, found 412.0. Anal. Calcd for C20H24N6S2: C,
58.22; H, 5.86; N, 20.37. Found: C, 58.01; H, 6.04; N, 20.12.
EXPERIMENTAL SECTION
■
Syntheses and Characterizations of the Intermediate Ma-
terial 1-Bromo-2-hexanone and Heterocyclic Aromatic Com-
pounds 2TZ, 2Br2TZ, 2Im2TZ, 2Py2TZ, 2T2TZ, 2TPA2TZ,
2BA2TZ, and 2EB2TZ. Compound 1-bromo-2-hexanone: This
compound was synthesized according to the previously reported
literature12a by minor modifications. Bromine (15.5 g, 5.0 mL, 97.1
mmol) was added dropwise to a stirred solution of 2-hexanone (9.72 g,
97.1 mmol) in methanol (60 mL) at −10 °C. The mixture was then
stirred at 0 °C for 45 min followed by 45 min at room temperature.
Water (30 mL) and then concentrated sulfuric acid (50 mL) were
added, and the mixture was stirred overnight at room temperature.
Water (90 mL) was added, and the mixture was extracted with ether
(4 × 50 mL). The combined extracts were washed with aqueous
sodium bicarbonate (50 mL) and water (2 × 50 mL). The extracts
were dried by anhydrous magnesium sulfate, the solvent was
evaporated, and the residue was distilled under reduced pressure to
give the compound 1-bromo-2-hexanone (7.28 g, 42%): bp 73−78 °C
1
(18 mgHg); H NMR (500 MHz, CDCl3) δ: 3.89 (s, 2H, CH2Br),
2Py2TZ. A degassed three-necked flask containing 2Br2TZ (1.10 g,
2.50 mmol), 4-pyridineboronic acid (0.75 g, 6.00 mmol), [Pd(PPh3)4]
(0.12 g, 0.10 mmol), and Cs2CO3 (2.70 g, 8.00 mmol) was dissolved
in a degassed mixture of dioxane (50 mL) and H2O (5 mL). The
mixture was stirred and refluxed under argon for 48 h. After the
mixture was cooled to room temperature, CHCl3 (100 mL) was
added, and the organic phase was washed with brine, separated, and
dried over anhydrous MgSO4. The organic solvent was evaporated
under reduced pressure and the solid residue was purified by silica gel
column chromatography using chloroform as an eluent to provide the
desired product 2Py2TZ as light yellow solid in a yield of 0.98 g
(90%). The yellow single crystals of 2Py2TZ suitable for X-ray
diffraction determination were grown from a solution of CHCl3 by
slow evaporation in air at room temperature for 5 days. Mp: 253−255
°C. Main FT-IR absorptions (KBr pellets, cm−1): 3413 (b), 2927 (m),
2.66 (t, 2H, butyl), 1.59 (m, 2H, butyl), 1.33 (m, 2H, butyl), 0.92 (t,
3H, butyl).
Caution! Although no problem was encountered in all our
experiments, the compound 1-bromo-2-hexanone is a kind volatile
chemical like tear gas and should be handled carefully.
2TZ. This compound was synthesized according to the previously
reported literature12b by minor modifications. 1-Bromo-2-hexanone
(1.98 g, 11.0 mmol), dithiooxamide (0.60 g, 5.0 mmol), and ethanol
(30 mL) were placed in a 100 mL, two-necked, round-bottom flask
equipped with a reflux condenser. The solution was heated to reflux
for 6 h, and after cooling, it was poured onto the crushed ice. The
mixture was extracted with dichloromethane and then dried over
anhydrous sodium sulfate. After evaporation of the solvent, the
product was obtained as a pale yellow solid in 94%. Yield (1.32 g). The
colorless single crystals of 2TZ suitable for X-ray diffraction
measurement were obtained from hexane and dichloromethane
(1:1) by slow evaporation in air at room temperature for 2 days.
Mp: 64−68 °C. Main FT-IR absorptions (KBr pellets, cm−1): 3421
(b), 3086 (m), 2955 (s), 2855 (s), 1647 (w), 1506 (s), 1456 (m),
1391 (s), 870 (s), 755 (m), 720 (m). 1H NMR (500 MHz, CDCl3) δ:
6.97 (s, 2H, thiazole), 2.83 (t, 4H, butyl), 1.70 (m, 4H, butyl), 1.38
(m, 4H, butyl), 0.96 (t, 6H, butyl). 13C NMR (125 MHz, CDCl3) δ:
160.8, 159.1, 114.5, 31.3, 31.2, 22.3, 13.8. EI-TOF-MS (m/z): calcd for
[C14H20N2S2]+ 280.4, found 280.1. Anal. Calcd for C14H20N2S2: C,
59.96; H, 7.19; N, 9.99. Found: C, 60.32; H, 7.41; N, 9.76.
2Br2TZ. This compound was synthesized according to the
previously reported literature12c by minor modifications. Compound
2TZ (1.40 g, 5.00 mmol) and NBS (1.80 g, 10.1 mmol) were dissolved
in a mixture of acetic acid (30 mL) and N,N-dimethylformamide
(DMF, 30 mL). After 4 h of stirring in the dark, a solid precipitated in
the reaction mixture. The precipitate was filtered, washed with
methanol, and then dried to produce compound 2Br2TZ as white
needles after recrystallization from CH2Cl2/hexane (2.02 g, 92%). The
colorless single crystals of 2Br2TZ suitable for X-ray diffraction
measurement were obtained from dichloromethane by slow
1
1589 (vs), 1543 (w), 1478 (w), 1475 (m), 1407 (m), 819 (m). H
NMR (500 MHz, CDCl3): δ 8.70 (dd, 4H, J = 6.0, 1.4 Hz, pyridine),
7.40 (dd, 4H, J = 6.0, 1.4 Hz, pyridine), 2.88 (t, 4H, n-butyl), 1.60 (m,
4H, n-butyl), 1.37 (m, 4H, n-butyl), 0.93 (t, 6H, n-butyl). 13C NMR
(125 MHz, CDCl3): δ 159.7, 156.1, 150.3, 139.8, 131.4, 123.5, 31.8,
29.7, 22.6, 13.9. EI-TOF-MS (m/z): calcd for [C24H26N4S2]+ 434.6,
found 434.0. Anal. Calcd for C24H26N4S2: C, 66.32; H, 6.03; N, 12.89.
Found: C, 66.11; H, 6.24; N, 12.67.
2T2TZ. To a suspension of magnesium (0.38 g, 16.0 mmol) in
anhydrous THF (10 mL), a solution of 2-bromothiophene (2.60 g,
16.0 mmol) in anhydrous THF (10 mL) was added dropwise. The
freshly prepared Grignard reagent was then added dropwise to an ice-
cooled suspension of compound 2Br2TZ (1.75 g, 4.00 mmol) and
[NiCl2(dppp)] (100 mg) in anhydrous THF (30 mL). The reaction
mixture was stirred for 20 h at room temperature. It was then
hydrolyzed with a saturated aqueous ammonium chloride solution, and
this was followed by the addition of CHCl3 (100 mL). The red organic
layer was washed with water (4 × 50 mL) and dried over anhydrous
sodium sulfate. The product 2T2TZ was finally separated by silica gel
column chromatography using hexane and dichloromethane (v/v =
H
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Article
1:1) as the eluent. After the removal of solvent and recrystallization
from the same solvents, the yellow product was obtained in a yield of
0.95 g (53%). Mp: 207−210 °C. Main FT-IR absorptions (KBr pellets,
cm−1): 3418 (b), 2950 (m), 2921 (m), 2858 (w), 2351 (w), 1644 (m),
CDCl3) δ: 8.12 (d, 4H, J = 8.2 Hz, phenyl), 7.55 (d, 4H, J = 8.1 Hz,
phenyl), 4.41 (q, 4H, OCH2), 2.85 (t, 4H, n-butyl), 1.76 (m, 4H, n-
butyl), 1.42 (t, 6H, ethyl), 1.36 (m, 4H, n-butyl), 0.90 (t, 6H, n-butyl).
13C NMR (125 MHz, CD3OD) δ: 166.1, 159.2, 155.0, 136.4, 133.1,
130.0, 129.2, 61.2, 31.9, 29.6, 22.5, 14.4, 13.9. EI-TOF-MS (m/z):
calcd for [C32H36N2O4S2]+ 576.8, found 576.2. Anal. Calcd for
C32H36N2O4S2: C, 66.64; H, 6.29; N, 4.86. Found: C, 65.46; H, 6.35;
N, 4.62.
1
1493 (w), 1459 (w), 1396 (w), 1050 (w), 689 (m). H NMR (500
MHz, CDCl3): δ 7.38 (dd, 2H, J = 5.1, 0.8 Hz, thiophene), 7.20 (dd,
2H, J = 3.6, 0.8 Hz, thiophene), 7.10 (dd, 2H, J = 5.1, 3.6 Hz,
thiophene), 2.95 (t, 4H, n-butyl), 1.77 (m, 4H, n-butyl), 1.44 (m, 4H,
n-butyl), 0.95 (t, 6H, n-butyl). 13C NMR (125 MHz, CDCl3): δ 157.8,
154.5, 133.0, 127.7, 127.4, 126.5, 114.8, 31.6, 30.0, 22.6, 13.9. EI-TOF-
MS (m/z): calcd for [C22H24N2S4]+ 444.7, found 443.9. Anal. Calcd
for C22H24N2S4: C, 59.42; H, 5.44; N, 6.30. Found: C, 59.17; H, 5.81;
N, 6.08.
X-ray Data Collection and Structural Determination. Single-
crystal samples of seven compounds 2TZ, 2Br2TZ, 2Im2TZ,
2Py2TZ, 2T2TZ, 2BA2TZ·(DMF)2, and 2EB2TZ were covered
with glue and mounted on glass fibers and then used for data
collection. Crystallographic data were collected on a Bruker SMART
1K CCD diffractometer, using graphite monochromated Mo Kα
radiation (λ = 0.71073 Å). The crystal systems were determined by
Laue symmetry, and the space groups were assigned on the basis of
systematic absences using XPREP.24 Absorption corrections were
performed to all data and the structures were solved by direct methods
2TPA2TZ. A mixture of compound 2Br2TZ (0.44 g, 1.00 mmol),
4-(diphenylamino)phenylboronic acid (1.16 g, 4.00 mmol), cesium
carbonate (1.30 g, 4.00 mmol), [Pd(PPh3)4] (0.06 g, 0.05 mmol),
toluene (12 mL), and water (3 mL) was degassed for 0.5 h and heated
to reflux for 40 h under an argon atmosphere. The mixture was then
allowed to cool to room temperature and extracted with chloroform.
The resulting organic layer was dried over anhydrous sodium sulfate
and filtered. The filtrate was evaporated, and the residue was purified
by column chromatography over silica gel using hexane and
dichloromethane (v/v = 1:1) as the eluent to give 0.56 g (73%) of
compound 2TPA2TZ as light yellow solid. Mp: 367−370 °C. Main
FT-IR absorptions (KBr pellets, cm−1): 3413 (m), 2956 (m), 1589 (s),
1487 (vs), 1330 (m), 1278 (s), 754 (m), 698 (m), 514 (m). 1H NMR
(500 MHz, CDCl3) δ: 7.31 (d, 4H, J = 8.2 Hz, triphenylamino), 7.29
(t, 8H, triphenylamino), 7.15 (d, 8H, J = 7.8 Hz, triphenylamino), 7.09
(d, 4H, J = 8.7 Hz, triphenylamino), 7.07(t, 4H, triphenylamino), 2.83
(t, 4H, n-butyl), 1.76 (m, 4H, n-butyl), 1.40 (m, 4H, n-butyl), 0.91 (t,
6H, n-butyl). 13C NMR (125 MHz, CDCl3) δ: 147.3, 130.0, 129.4,
125.0, 123.5, 122.6, 32.0, 29.4, 22.5, 13.9. EI-TOF-MS (m/z): calcd for
[C50H46N4S2]+ 766.3(100.0), 767.3(56.2), found 766.1(100.0),
767.2(47.8). Anal. Calcd for C50H46N4S2: C, 78.29; H, 6.04; N, 7.30.
Found: C, 77.89; H, 6.51; N, 7.12.
2BA2TZ. A degassed three-necked flask containing 2Br2TZ (0.88
g, 2.00 mmol), 4-boronobenzoic acid (0.73 g, 4.40 mmol),
[Pd(PPh3)4] (0.12 g, 0.10 mmol), and Cs2CO3 (1.95 g, 6.00 mmol)
was dissolved in a degassed mixture of dioxane (50 mL) and H2O (5
mL). The mixture was stirred and refluxed under argon for 48 h. After
being cooled to room temperature, the light yellow solid was obtained
in the reaction mixture. The precipitate was filtered, washed with
CHCl3 and methanol, and then dried in vacuo to produce compound
2BA2TZ in a yield of 0.92 g (89%). The yellow single crystals of
2BA2TZ·(DMF)2 suitable for X-ray diffraction measurement were
obtained from DMF by slow evaporation in air at room temperature
for 3 weeks. Mp: 201−203 °C. Main FT-IR absorptions (KBr pellets,
cm−1): 3404 (m), 3138 (s), 3045 (s), 2958 (s), 1693 (m), 1604 (m),
1407 (vs), 1265 (m), 781 (w). 1H NMR (500 MHz, CD3OD) δ: 8.06
(d, 4H, J = 7.8 Hz, phenyl), 7.54 (d, 4H, J = 8.0 Hz, phenyl), 2.85 (t,
4H, n-butyl), 1.75 (m, 4H, n-butyl), 1.36 (m, 4H, n-butyl), 0.91 (t, 6H,
n-butyl). 13C NMR (125 MHz, CD3OD) δ: 173.2, 158.6, 154.0, 138.0,
134.2, 133.0, 129.4, 128.5, 31.5, 28.8, 22.0, 12.7. EI-TOF-MS (m/z):
calcd for [C28H28N2O4S2]+ 520.7, found 520.1. Anal. Calcd for
C28H28N2O4S2: C, 64.59; H, 5.42; N, 5.38. Found: C, 64.27; H, 5.68;
N, 5.12.
2
and refined by full-matrix least-squares method on Fobs by using the
SHELXTL-PC software package.25 All non-H atoms were anisotropi-
cally refined and all hydrogen atoms were inserted in the calculated
positions assigned fixed isotropic thermal parameters and allowed to
ride on their respective parent atoms. The summary of the crystal data,
experimental details and refinement results for seven compounds is
listed in Table 2, whereas bond distances and angles are given in Table
SI1 (Supporting Information). In addition, hydrogen-bonding
parameters are tabulated in Table SI2 (Supporting Information).
Computational Details. All calculations were carried out with
Gaussian 09 programs.19 The geometries of molecules 2TZ, 2Br2TZ,
2Im2TZ, 2Py2TZ, 2T2TZ, 2BA2TZ, 2EB2TZ and their respective
bithiophene counterparts (see the Supporting Information) were fully
optimized and calculated by the B3LYP method and 6-31G* basis set
without any symmetry constraints. The single-crystal structures were
used as the starting geometries, while other input files were obtained
by the substituent-modified approach based on the earlier output files.
For computational simplicity, the n-butyl chains are replaced by the
methyl groups since this replacement is not expected to alter the
results and the trends significantly.20
ASSOCIATED CONTENT
■
S
* Supporting Information
Tables of selected bond lengths and angles and intermolecular
hydrogen bonds, figures of π−π stacking interactions, H, 13C,
1
1
1H−1H, and H−13C COSY NMR and EI-TOF-MS spectra,
DFT computational details, and electrochemistry diagrams for
related compounds. CCDC nos. 914949−914955 for 2TZ,
2Br2TZ, 2Im2TZ, 2Py2TZ, 2T2TZ, 2BA2TZ, and 2EB2TZ.
This material is available free of charge via the Internet at
http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: whuang@nju.edu.cn.
■
Notes
2EB2TZ. A mixture of compound 2BA2TZ (0.52 g, 1.00 mmol),
sodium hydroxide (0.16 g, 4.00 mmol), and ethanol (30 mL) was
refluxed for 15 h under argon atmosphere. The mixture was then
allowed to cool to room temperature and extracted with chloroform.
The resulting organic layer was dried over anhydrous sodium sulfate
and filtered. The organic solvent was evaporated under reduced
pressure, and the solid residue was purified by silica gel column
chromatography using chloroform as an eluent to give 0.39 g (68%)
yellow solid of compound 2EB2TZ. The yellow single crystals of
2EB2TZ suitable for X-ray diffraction determination were grown from
an ethanol solution of sodium hydroxide (10%) by slow evaporation in
air at room temperature for 2 weeks. Mp: 171−174 °C. Main FT-IR
absorptions (KBr pellets, cm−1): 3401 (b), 2946 (m), 1720 (s), 1606
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was financially supported by the Major State Basic
Research Development Programs (Nos. 2013CB922101,
2011CB933300, and 2011CB808704), the National Natural
Science Foundation of China (Nos. 21171088 and 21021062),
and the Qing Lan Project.
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Article
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