Article

Cite This: J. Org. Chem. 2018, 83, 8114−8126 pubs.acs.org/joc

Construction of 3,7-Dithienyl Phenothiazine-Based Organic Dyes via

Multistep Direct C−H Arylation Reactions
Wen Wang,† Xiaoyu Li,‡ Jingbo Lan,*,† Di Wu,† Ruilin Wang,*,§ and Jingsong You†
†
Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, Sichuan University, 29
Wangjiang Road, Chengdu 610064, China
‡
Fundamental Science on Nuclear Wastes and Environmental Safety Laboratory, Southwest University of Science and Technology,
Mianyang 621010, China
§
College of Materials Science and Engineering, Sichuan University, 29 Wangjiang Road, Chengdu 610064, China
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*
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S Supporting Information

ABSTRACT: Herein, an effective and feasible approach to prepare 3,7-dithienyl

phenothiazine-based organic dyes has been developed. In this synthetic procedure,
the Pd-catalyzed multistep direct C−H arylation of thiophene derivatives with
phenothiazine bromides was employed for the first time to construct the 3,7-
dithienyl phenothiazine core scaffold, which greatly streamlines access to this class
of organic dyes. 3-Thienyl phenothiazine-based dyes were also synthesized via the
direct C−H arylation of thiophenes as references. Most of the 3,7-dithienyl
phenothiazine-based dyes exhibit better photovoltaic performances than the 3-
thienyl phenothiazine-based dyes. Among these organic dyes, the solar cell device
based on 6d exhibits the highest conversion efficiency of 8.9%. Compared with 6d,
organic dyes with longer π-conjugation, also including bithiophene as the π-spacer,
show dramatically reduced conversion efficiencies of cell devices. The introduction
of the more electron-rich 3,4-ethylenedioxythiophene to the C3- and/or C7-
position of phenothiazine instead of thiophene does not significantly improve the photoelectric conversion performance. The
highly efficient synthetic strategy herein developed and these primary results may be helpful to design and synthesize a variety of
new 3,7-dithienyl phenothiazine-based organic dyes.

■ INTRODUCTION
Metal-free organic dyes for dye-sensitized solar cells (DSSCs)
have gained widespread attention in recent years due to their
low cost, easy preparation and purification, and structural
flexibility.1 The construction of a donor−π−acceptor (D−π−
A) structure is a common principle in the design of organic
dyes for DSSCs, in which a 2-cyanoacrylic acid or rhodanine
unit usually renders the acceptor functionality and furthermore
is used as an anchoring group.1f,2 Most of the electron-rich
units can be employed as electron donors. Phenothiazine
possesses a nonplanar heteroanthracene structure with a
butterfly conformation, which can serve to inhibit the dye
aggregation and the excimer formation.3 Moreover, the
electron-rich sulfur and nitrogen atoms located in the middle
ring endow phenothiazine a strong electron-donating ability.4
Therefore, phenothiazine has been widely used as an electron
donor to develop organic dyes in recent years.5 In addition, it is
well-known that the selection of a suitable π-conjugated spacer
between the donor and the acceptor is very important in the
design of organic dyes.6 Thiophenes possess thermal stability,
aromaticity, and a slightly electron-rich characteristic and thus
are widely employed as π-spacers in organic dyes, which are
usually preferable to extend π-conjugation and promote the
efficient intramolecular charge transfer (ICT).6,7
In recent years, organic dyes based on a phenothiazine
electron donor and a thiophene π-spacer have been developed
and exhibit promising performances.6b,8 Traditional methods to
connect the phenothiazine unit and the thiophene unit mainly
rely on Stille or Suzuki coupling reaction.8 These methods
generally suffer from limitations, including tedious synthetic
steps to prepare organoboron or organotin reagents, using
highly toxic trimethyltin chloride or tributyltin chloride, and a
stoichiometric amount of toxic byproducts. Undoubtedly,
transition-metal-catalyzed direct C−H arylation is an ideal
strategy to accomplish the coupling between phenothiazine and
thiophene.9 This strategy avoids the time-consuming prefunc-
tionalization of thiophene, including the regioselective halo-
genation, the lithiation, as well as the subsequent reaction with
borate esters or trialkyltin chlorides, and thus greatly simplifies
the operation processes and reduces the unnecessary wastes.
The effect of various thiophene π-spacers, including thiophene,
bithiophene, 3,4-ethylenedioxythiophene (EDOT), etc., on
DSSC performances has not been studied systematically so
far, due to the lack of rapid, general routes to connect
phenothiazine with thiophene. Once a concise and reliable
pathway toward the connection between phenothiazine and
Received: April 11, 2018
Published: May 31, 2018

© 2018 American Chemical Society 8114 DOI: 10.1021/acs.joc.8b00915

J. Org. Chem. 2018, 83, 8114−8126
The Journal of Organic Chemistry Article

Scheme 1. Synthetic Routes to 3,7-Dithienyl Phenothiazine-Based Organic Dyesa

a
Reaction conditions: (i) Pd(OAc)2, PCy3·HBF4, PivOH, K2CO3, toluene, 110 °C, 24 h; (ii) N-bromosuccinimide, DMF, 0−25 °C, 12 h; (iii)
Pd(OAc)2, PCy3·HBF4, PivOH, K2CO3, toluene, 110 °C, 24 h; (iv) cyanoacetic acid, piperidine, chloroform, 80 °C, 6 h. Cy = cyclohexyl, DMF =
N,N-dimethyl formamide, PivOH = pivalic acid.

Table 1. Optimization of the Direct C−H Arylation of 2a with 1aa

entry catalyst ligand base solvent temperature yield (%)

1 PdCl2 PCy3·HBF4 K2CO3 toluene 110 °C 62
2 Pd(PPh3)2Cl2 PCy3·HBF4 K2CO3 toluene 110 °C 5
3 Pd(OAc)2 PCy3·HBF4 K2CO3 toluene 110 °C 89
4b Pd(OAc)2 PCy3·HBF4 K2CO3 toluene 110 °C 60
5 Pd(TFA)2 PCy3·HBF4 K2CO3 toluene 110 °C 65
6 Pd(OAc)2 P(t-Bu)3·HBF4 K2CO3 toluene 110 °C 48
7 Pd(OAc)2 PPh3 K2CO3 toluene 110 °C 42
8 Pd(OAc)2 PCy3·HBF4 Cs2CO3 toluene 110 °C 30
9 Pd(OAc)2 PCy3·HBF4 Na2CO3 toluene 110 °C 11
10 Pd(OAc)2 PCy3·HBF4 NaOAc toluene 110 °C 3
11 Pd(OAc)2 PCy3·HBF4 K2CO3 dioxane 110 °C 54
12 Pd(OAc)2 PCy3·HBF4 K2CO3 DMF 110 °C 59
13c Pd(OAc)2 PCy3·HBF4 K2CO3 toluene 110 °C 66
14 Pd(OAc)2 PCy3·HBF4 K2CO3 toluene 100 °C 82
15 Pd(OAc)2 PCy3·HBF4 K2CO3 toluene 120 °C 64
a
Reaction conditions: 3-bromo-10-hexyl-10H-phenothiazine (1a, 0.5 mmol, 1.0 equiv), thiophene-2-carbaldehyde (2a, 0.75 mmol, 1.5 equiv),
catalyst (5 mol %), ligand (10 mol %), base (0.75 mmol, 1.5 equiv), PivOH (30 mol %), solvent (1.5 mL), 110 °C, 24 h. Isolated yield. bIn the
absence of pivalic acid. cBase (1.5 mmol, 3.0 equiv).

thiophene has been established, it would provide opportunities
for the rapid construction of a series of various phenothiazine−
thiophene D−π−A structures for screening high performance
organic dyes. Following our continuing interest in C−H bond
activation and functionalization,10,11 we herein present the first
example of the Pd-catalyzed multistep direct C−H arylation of
thiophene derivatives to prepare the organic dyes based on 3,7-
dithienyl phenothiazine D−π−A structures and the inves-
tigation of their photophysical, electrochemical, and photo-
voltaic properties (Scheme 1).
as an additive under a N2 atmosphere (Table 1, entry 3). In the
absence of pivalic acid, 3a could be obtained with a yield of 60%
(Table 1, entry 4). Upon addition of 30 mol % pivalic acid to
this catalytic system with an excess of potassium carbonate, 3a
was obtained in 89% yield (Table 1, entry 3), where potassium
pivalate could be generated in situ. The pivalate might serve as
a soluble proton transfer agent from the thiophene and
palladium catalyst to the insoluble carbonate salt.12 Therefore,
we deduced that the concerted metalation−deprotonation
(CMD) pathway promoted by pivalate might result in the

■
RESULTS AND DISCUSSION
Our investigation began with the direct C−H arylation of
thiophene-2-carbaldehyde (2a) with 3-bromo-10-hexyl-10H-
phenothiazine (1a) by using PdCl2 in conjunction with PCy3·
HBF4 ligand (Table 1, entry 1). Delightedly, the direct arylation
product 3a was obtained in 62% yield. After screening other
catalysts, ligands, bases, solvents, additives, and reaction
temperatures, the best result was obtained in toluene at 110
°C for 24 h with 5 mol % Pd(OAc)2 as a catalyst, PCy3·HBF4 as
a ligand, K2CO3 as a base, and pivalic acid (PivOH, 30 mol %)
8115
increased reactivity.
Under the optimal conditions, 5-(10-hexyl-10H-phenothia-
zin-3-yl)thiophene-2-carbaldehyde (3a), 5-(10-hexyl-10H-phe-
nothiazin-3-yl)-3,4-ethylenedioxythiophene-2-carbaldehyde
(3b), and 5′-(10-hexyl-10H-phenothiazin-3-yl)-[2,2′-bithio-
phene]-5-carbaldehyde (3c) were synthesized through the
direct C−H arylation reaction as dye precursors for further
modifications (Scheme 2). It is worth noting that 3a could be
obtained not only with a yield of 89% by loading 0.5 mmol of
1a but also with a high yield of 83% on a gram scale (12.0
mmol). Replacing brominated phenothiazine with brominated
triphenylamine and carbazole, the direct C−H arylation
DOI: 10.1021/acs.joc.8b00915
J. Org. Chem. 2018, 83, 8114−8126
The Journal of Organic Chemistry
Scheme 2. Synthesis of Thienyl Phenothiazine,
Triphenylamine, and Carbazole Derivatives via the Direct
C−H Arylation of Thiophenesb
a
Gram scale. bReaction conditions: 1 (0.5 mmol, 1.0 equiv), 2 (0.75
mmol, 1.5 equiv), Pd(OAc)2 (5 mol %), PCy3·HBF4 (10 mol %),
PivOH (30 mol %), K2CO3 (0.75 mmol, 1.5 equiv), toluene (1.5 mL),
110 °C, 24 h under a N2 atmosphere. Isolated yield.
reaction still worked well, affording N,N-diphenyl-4-(thiophen-
2-yl)aniline (3d) and 9-hexyl-3-(thiophen-2-yl)-9H-carbazole
(3e) in good yields.
Next, the bromination of 3-thienyl phenothiazines was
carried out. Owing to the absence of the competitive reaction
of the C2-position of thienyl groups, the bromination reaction
mainly took place at the C7-position of phenothiazines,
providing the brominated 3-thienyl phenothiazine derivatives
4a, 4b, and 4c in 78, 75, and 68% yields, respectively (Scheme
3).
Utilizing the direct C−H arylation of thiophenes once again,
a series of 3,7-dithienyl phenothiazine derivatives (5a−5l) were
obtained in moderate to good yields (Scheme 4). Subsequently,
Scheme 3. Bromination of 3-Thienyl Phenothiazinesa
a
Reaction conditions: 3 (8 mmol, 1.0 equiv), N-bromosuccinimide
(NBS, 8.8 mmol, 1.1 equiv), DMF (45 mL), 0−25 °C, 12 h. Isolated
yield.
8116
Article
the Knövenagel condensations of 5 with cyanoacetic acid were
performed in the presence of piperidine in CHCl3 to prepare
the 3,7-dithienyl phenothiazine-based organic dyes (6a−6l)
(Scheme 5). 3-Thienyl phenothiazine-based organic dyes 6m
and 6n were also synthesized as references.
With a divergent library of 3,7-dithienyl phenothiazine-based
organic dyes in hand, we subsequently investigated their
photophysical and electrochemical properties. Figure 1 shows
the UV−vis absorption spectra of each dye in dichloromethane
solution (2 × 10−5 M) and adsorbed on TiO2 film, and the
detailed parameters including the wavelength of maximum
absorption (λmax), the molar extinction coefficient (ε), and the
absorption onset (λonset) of these dyes are summarized in Table
2.
The UV−vis absorption spectra of these organic dyes in
CH2Cl2 (2 × 10−5 M) exhibit two absorption bands, appearing
at 300−410 and 410−600 nm, which are assigned to the
localized π−π* transitions of the chromophores and the
charge-transfer (CT) transition from the donor to the acceptor,
respectively (Figure 1a). Compared with 3-thienyl phenothia-
zine-based organic dyes (6m and 6n), the short-wavelength
absorption of the π−π* transitions of 3,7-dithienyl phenothia-
zine-based dyes (6a−6l) is enhanced due to the extended
conjugation length. The dye 6n shows higher extinction
coefficients in CT absorption than 6m due to the extended
conjugation length. The dyes 6a−6l show lower molar
extinction coefficients in CT transitions than 6n, which might
be attributed to the nonplanarity of the additional donor
including triphenylamine and carbazole that enhances geo-
metric twisting of molecules.13 In 6a−6l, the molar extinction
coefficients of the CT transition of dyes are slightly enhanced
with an increased electron-donating capability of π-spacer or an
extended π-conjugation length (for example, the molar
extinction coefficients: 6b > 6a, 6f > 6e > 6d, 6h > 6g, and
6k > 6j). When these dyes are adsorbed on TiO2 films,
although the wavelengths of maximum absorptions are slightly
blue-shifted with respect to their solutions due to the
deprotonation of carboxylic acids, their absorption thresholds
are remarkably red-shifted to above 650 nm, which matches
well with the visible region of the solar spectrum (Figure 1b).
The electrochemical properties of these organic dyes (6a−
6n) were investigated via cyclic voltammetry to evaluate the
possibility of the electron injection from the photoexcited dyes
to the conduction band (CB) of TiO2 and the dye regeneration
(Table 2 and Figure S1). Most of the dyes show more than one
oxidation potential due to the presence of an additional donor,
and the first and second oxidation potentials of dyes are listed
in Table 2. The first oxidation potentials (Eox) of 6a−6n range
from 0.72 to 0.89 V (vs NHE), which correspond to the highest
occupied molecular orbital (HOMO) of molecules. Their
zero−zero band gaps (E0−0) were estimated from the onset of
the absorption spectra, which are between 1.90 and 2.01 eV.
The excited-state oxidation potentials (Eox*), calculated from
Eox − E0−0, correspond to the lowest unoccupied molecular
orbital (LUMO), which ranges from −1.12 to −1.23 V. The
HOMO levels of all of these dyes are much more positive than
the iodine/iodide redox potential value (0.42 V vs NHE),
ensuring that the oxidized dyes can be regenerated by the I−/
I3− electrolyte. Similarly, the LUMO levels of 6a−6n are
sufficiently more negative than the conduction-band-edge
energy level (ECB) of the TiO2 photoanode (−0.5 V vs
NHE), implying the feasibility of electron injection from the
photoexcited dyes into the CB of TiO2.
DOI: 10.1021/acs.joc.8b00915
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The Journal of Organic Chemistry Article

Scheme 4. Synthesis of 3,7-Dithienyl Phenothiazine Derivatives via the Direct C−H Arylation of Thiophenesa

a
Reaction conditions: 4 (0.5 mmol, 1.0 equiv), 2 or 3 (0.75 mmol, 1.5 equiv), Pd(OAc)2 (5 mol %), PCy3·HBF4 (10 mol %), K2CO3 (0.75 mmol,
1.5 equiv), PivOH (30 mol %), toluene (2 mL), 110 °C, 24 h. Isolated yield.

Scheme 5. Preparation of 3,7-Dithienyl Phenothiazine-Based Organic Dyes via Knövenagel Condensationa

a
Reaction conditions: 3 or 5 (0.25 mmol, 1.0 equiv), cyanoacetic acid (0.75 mmol, 3.0 equiv), piperidine (0.75 mmol, 3.0 equiv), CHCl3 (2 mL),
reflux, 6 h. Isolated yield.

The DSSCs with an active area of 0.4 × 0.4 cm2 were
fabricated using TiO2 photoanodes sensitized with organic dyes
(6a−6n), electrodeposited platinum counter electrodes, and an
I−/I3− redox couple as the electrolyte. Considering that the
solvent may make a difference for the photovoltaic properties of
DSSC devices,14 the optimization of the device fabrication
process with different solvents is provided in the Supporting
Information (section II). The photovoltaic parameters were
measured under an irradiance of AM 1.5G sunlight (100 mW
8117
cm−2), and the photocurrent−voltage (J−V) plots are shown in
Figure 2a. The solar cell of 3-thienyl phenothiazine-based
organic dye 6m exhibits a relatively low conversion efficiency of
5.25%.15 Replacing thiophene with bithiophene to extend the
π-bridge, the conversion efficiency of the cell based on 6n
increases to 6.91%. Introducing electron-donating units, such as
5-(4-(diphenylamino)phenyl)thiophen-2-yl, 5-(9H-carbazol-9-
yl)thiophen-2-yl, 5-(9H-carbazol-9-yl) 3,4-ethylenedioxythio-
phen-2-yl, 5-(9-hexyl-9H-carbazol-3-yl)thiophen-2-yl, 3,4-ethyl-
DOI: 10.1021/acs.joc.8b00915
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The Journal of Organic Chemistry Article

Figure 1. Absorption spectra of 6a−6n (a) in CH2Cl2 (2 × 10−5 M) and (b) anchored on 3 μm transparent TiO2 films.

Table 2. Photophysical and Electrochemical Properties of 6a−6n

dyes λmax (nm) (ε × 104 M−1 cm−1)a λonsetb (nm) Eoxc (V) E0−0d (eV) Eox* e (V)
6a 370 (3.80) 470 (1.75) 642 0.81 1.24 1.93 −1.12
6b 376 (3.76) 484 (2.24) 630 0.75 1.27 1.97 −1.22
6c 381 (3.27) 634 0.72 1.32 1.96 −1.23
6d 361 (2.45) 481 (2.19) 627 0.81 1.03 1.98 −1.17
6e 369 (2.13) 495 (2.51) 632 0.78 1.04 1.96 −1.18
6f 388 (2.06) 467 (2.57) 616 0.89 1.01 2.01 −1.12
6g 365 (2.89) 490 (2.50) 638 0.77 1.02 1.94 −1.17
6h 368 (2.36) 498 (2.78) 643 0.80 1.03 1.93 −1.13
6i 364 (3.38) 462 (2.06) 633 0.78 1.00 1.96 −1.18
6j 362 (1.94) 480 (1.71) 641 0.73 1.02 1.93 −1.20
6k 372 (1.52) 486 (1.97) 652 0.72 1.02 1.90 −1.18
6l 361 (2.26) 490 (2.01) 653 0.77 1.35 1.90 −1.13
6m 373 (1.46) 478 (2.20) 636 0.78 1.94 −1.16
6n 490 (3.14) 642 0.80 1.04 1.93 −1.13
a
Absorption maxima (λmax) and molar extinction coefficients (ε) were measured in CH2Cl2 (2 × 10−5 M). bAbsorption onset (λonset) of sensitizers.
c
Oxidation potential was measured in DMSO containing 0.1 M n-Bu4NPF6 with a scanning rate of 50 mV s−1 (vs NHE). dE0−0 = 1240/λonset. eEox* =
Eox − E0−0.

Figure 2. (a) J−V plots under simulated AM 1.5G irradiation. (b) IPCE curves.

enedioxythiophen-2-yl (EDOT), and 5-hexyl-EDOT, to the
C7-position of the phenothiazine of 6m results in increased
conversion efficiencies in varying degrees (Table 3, 6a, 6d, 6g,
6i, 6j, and 6l). However, introducing the same electron-
donating units, such as 5-(4-(diphenylamino)phenyl)thiophen-
2-yl and 5-(9H-carbazol-9-yl)thiophen-2-yl, to the C7-position
of the phenothiazine of 6n leads to slightly reduced conversion
efficiencies (Table 3, 6c and 6f). Furthermore, replacing the
thiophene at the C3-position of the phenothiazine of 6a, 6d, 6g,
and 6j with EDOT, the resulting dyes 6b, 6e, 6h, and 6k exhibit
slightly reduced efficiencies of solar cells, except for 6h. The
conversion efficiency of the solar cell based on 6h is higher than
that based on 6g but slightly lower than that based on 6e.
Among these dyes, the cell based on 6d exhibits the highest
conversion efficiency of 8.9% (Jsc = 15.91 mA cm−2, Voc = 0.770
8118
V, FF = 0.727), which approximates to the efficiency of the
N719-based device (9.63%) under the same conditions. These
results demonstrate that the introduction of the more electron-
rich EDOT to the C3- and/or C7-position of phenothiazine
instead of thiophene cannot significantly improve the photo-
voltaic performance of the resulting organic dyes. Moreover,
compared with 6d, 6e, 6g, and 6h, the organic dyes 6a, 6b, 6c,
and 6f with longer π-conjugation show dramatically reduced
conversion efficiencies of solar cells, indicating that a greater
length of conjugation may induce larger dispersion forces
between the dyes and the acceptors, leading to short electron
lifetimes and thus lower Voc. In addition, the dyes with a greater
length of conjugation might form less trimly packed dye layers,
resulting in uncovered TiO2 areas and low dye loads.16
DOI: 10.1021/acs.joc.8b00915
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The Journal of Organic Chemistry Article

Table 3. Photovoltaic Performance of DSSC Devicesa Nyquist plots. In general, the larger radius of the semicircle
means larger Rrec and smaller electron recombination rate.17 As
PCE Rrec
dyes Voc (V) Jsc (mA cm−2) FF (%) (Ω) τe (ms) shown in Table 3, the order of Rrec is consistent with the order
of Voc. 6e exhibits the largest Rrec and thus the largest Voc. From
6a 0.726 12.66 0.724 6.66 46 6.1
the peak frequency (f) in the lower frequency region in EIS
6b 0.727 12.15 0.734 6.48 54 8.5
Bode phase plots (Figure 3b), the effective electron lifetime
6c 0.670 13.69 0.661 6.07 31 4.3
(τe) is obtained by τe = 1/(2πf) (Table 3).18 Longer lifetime
6d 0.770 15.91 0.727 8.90 70 20.1
means smaller electron recombination rate. The results of the
6e 0.784 14.79 0.735 8.53 77 23.1
electron lifetime are consistent with the values of Voc of devices.

■
6f 0.726 13.10 0.719 6.85 46 6.7
6g 0.736 14.72 0.711 7.70 58 9.4
6h 0.755 15.67 0.706 8.36 64 18.4
CONCLUSION
6i 0.694 13.59 0.632 6.05 45 5.5 In summary, we have developed an efficient and step-
6j 0.737 13.48 0.724 7.19 59 9.9 economical synthetic route to prepare phenothiazine-based
6k 0.667 14.38 0.660 6.33 25 3.5 organic dyes by Pd-catalyzed multistep direct C−H arylation of
6l 0.748 13.90 0.714 7.42 62 13.3 thiophene derivatives. On the basis of this synthetic strategy, a
6m 0.678 11.83 0.655 5.25 63 4.9 class of 3,7-dithienyl phenothiazine core scaffolds were
6n 0.750 14.36 0.642 6.91 64 16.9 constructed successfully. 3-Thienyl phenothiazine-based dyes
N719b 0.764 18.24 0.690 9.63 6m and 6n were also synthesized as references. The
a
J−V characteristics were measured under standard AM 1.5G photophysical, electrochemical, and photovoltaic properties of
irradiation (100 mW cm−2) with an effective working area of 0.4 × the resulting organic dyes (6a−6n) were systematically
0.4 cm2 at room temperature. TiO2 photoanode was dipped in 0.5 investigated. The incorporation of electron-donating units to
mmol/L dye solution (DCM/THF 9/1) for 12 h. TiO2 photoanode: the C7-position of the phenothiazine of 6m results in an
14 μm thick of 20 nm sized TiO2 transparent film with 5 μm thick of increase in the conversion efficiency of DSSCs. Among these
400 nm sized TiO2 light scattering layer. The electrolyte was dyes, the solar cell device based on 6d exhibits the highest
composed of 1.0 M DMPII, 0.1 M LiI, 0.05 M I2, and 0.5 M TBP conversion efficiency of 8.9% (Jsc = 15.91 mA cm−2, Voc = 0.770
with CH3CN as solvent. EIS was measured in dark conditions under a
forward bias of −0.70 V, and Rrec was fitted by Z-View software. bThe
V, FF = 0.727), which approximates to the efficiency of the
TiO2 photoanode was dipped in the solution of N719 (0.5 mmol/L) N719-based device (9.63%) under the same conditions. The
in CH3CN/t-BuOH (1:1) for 12 h. introduction of the more electron-rich EDOT to the C3- and/
or C7-position of phenothiazine instead of thiophene cannot
significantly improve the photoelectric conversion performance.
The incident photo-to-current conversion efficiencies
Compared with 6d, organic dyes with longer π-conjugation
(IPCE) of the DSSC devices are shown in Figure 2b. The
show dramatically reduced conversion efficiencies, indicating
IPCE curves of photosensitizers demonstrate that the light
that a great length of conjugation may induce a large dispersion
ranging from 350 to 650 nm can be converted to photocurrent
force between the dye and the acceptor, or a less trimly packed
effectively, which is consistent with the UV−vis absorption
dye layer, thus leading to low Voc and/or Jsc. We hope that the
spectra of the dyes adsorbed on TiO2 films. The maximum
highly efficient synthetic strategy herein developed and these
values of the IPCE of all sensitizers exceed 60%. Among these,
primary results will be helpful to design and synthesize a variety
6d exhibits the highest IPCE value of 87% and exceeds 80% in
of new 3,7-dithienyl phenothiazine-based organic dyes.

the spectra of 400−560 nm.
To get an elucidation of the difference of open-circuit
photovoltages in DSSCs based on these dyes, electrochemical
impedance spectroscopy (EIS) was performed in dark
conditions under a forward bias of −0.70 V. Figure 3a shows
the Nyquist plots of the DSSCs and their charge transfer
resistance (Rrec) values are listed in Table 3, which are fitted by
Z-View software according to a circuit diagram. The interfacial
charge recombination reaction at the TiO2/dye/electrolyte
interface can be described by Rrec, which corresponds to the
larger semicircle (occurs in the middle frequency range) of the
■
EXPERIMENTAL SECTION
General Information. 1H (400 MHz) and 13C (100 MHz) NMR
spectra were obtained on a Bruker AV II-400 MHz or an Agilent 400-
MR DD2 spectrometer. The 1H NMR chemical shifts were measured
relative to CDCl3 or DMSO-d6 as an internal reference (CDCl3, δ =
7.26 ppm; DMSO-d6, δ = 2.50 ppm). The 13C NMR chemical shifts
were given using CDCl3 or DMSO-d6 as an internal standard (CDCl3,
δ = 77.16 ppm; DMSO-d6, δ = 39.52 ppm). High-resolution mass
spectra (HRMS) were obtained with Waters-Q-TOF-Premier (ESI).
Cyclic voltammetry (CV) was performed on LK2005A. UV−vis-NIR

Figure 3. Electrochemical impedance spectroscopy (EIS) for DSSCs: (a) Nyquist plots; (b) Bode phase plots.

8119 DOI: 10.1021/acs.joc.8b00915

J. Org. Chem. 2018, 83, 8114−8126
The Journal of Organic Chemistry
absorption spectra were recorded on a SHIMADZU UV-3600
spectrophotometer.
Photoelectrochemical characterizations on the solar cells were
performed by employing an Oriel Class AAA solar simulator (Oriel
94023A, Newport Corp.). Photocurrent−voltage characteristics of the
DSSCs were obtained by a potentiostat/galvanostat (Keithley Series
2400 SourceMeter, Keithley Instruments, Inc.) at a light intensity of
100 mW cm−2 calibrated by an Oriel reference solar cell (Oriel
91150V, Newport Corp.). An IPCE test was performed by using a
Qtest Station 1000AD (Crowntech, Inc.) which has a xenon light
source and a monochromator (Czerny-Turner). The system is
equipped with a NIST traceable Si detector as a reference. A short
circuit photocurrent spectrum was recorded with a Keithley 2000
multimeter. Electrochemical impedance spectroscopy (EIS) was
recorded by a Solotron 1260 and 1287. Unless otherwise noted, all
reagents were obtained from commercial suppliers and used without
further purification.
The Pt-counter electrode and two types of TiO2 films were
purchased from OPV Tech (China). A 3 μm thick film of transparent
TiO2 films as the absorbing layer coated on a FTO glass substrate with
dimensions of 1.0 × 1.0 cm2 was used to test UV−vis spectra. A 14 μm
thick of 20 nm sized TiO2 transparent film with 5 μm thick of 400 nm
sized TiO2 light scattering layer coated on a FTO glass substrate with
dimensions of 0.4 × 0.4 cm2 was used to assemble DSSCs.
Synthesis of 3-Bromo-10-hexyl-10H-phenothiazine (1a).19 In a
Schlenk flask (250 mL), phenothiazine (10.4 g, 52.2 mmol) and KOH
(4.4 g, 78.3 mmol) were dissolved in DMSO (120 mL). After the
mixture was stirred for 1 h at room temperature, 1-bromohexane (9.3
mL, 62.7 mmol) was added by means of a syringe, and the solution
was stirred for 12 h. The mixture was dissolved in ethyl acetate and
washed with water and brine. The organic layer was dried over
anhydrous Na2SO4 and concentrated under a vacuum. The residue was
purified by column chromatography (silica gel, petroleum ether). 10-
Hexyl-10H-phenothiazine was afforded as a colorless oil (13.3 g, 90%
yield). 1H NMR (400 MHz, CDCl3): δ = 0.88 (t, J = 7.2 Hz, 3H),
1.28−1.32 (m, 4H), 1.40−1.47 (m, 2H), 1.77−1.82 (m, 2H), 3.84 (t, J
= 7.2 Hz, 2H), 6.85−6.92 (m, 4H), 7.12−7.17 (m, 4H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 14.1, 22.7, 26.8, 27.0, 31.6, 47.6, 115.5,
122.4, 125.0, 127.3, 127.5, 145.5 ppm.
In a Schlenk flask (250 mL), 10-hexyl-10H-phenothiazine (7.5 g,
26.5 mmol) was stirred in DMF (70 mL) and cooled to 0 °C. N-
Bromosuccinimide (NBS) (4.7 g dissolved in 30 mL of DMF) was
added dropwise. Then, the mixture was allowed to warm to room
temperature and keep stirring overnight. The mixture was dissolved in
ethyl acetate and washed with water and brine. The organic layer was
dried over anhydrous Na2SO4 and concentrated under a vacuum. The
residue was purified by silica gel column chromatography (petroleum
ether) to afford 3-bromo-10-hexyl-10H-phenothiazine as a colorless oil
(7.0 g, 72.9% yield). 1H NMR (400 MHz, CDCl3): δ = 0.87 (t, J = 7.2
Hz, 3H), 1.26−1.28 (m, 4H), 1.37−1.43 (m, 2H), 1.73−1.80 (m, 2H),
3.79 (t, J = 7.2 Hz, 2H), 6.68−6.70 (m, 1H), 6.83−6.86 (m, 1H),
6.90−6.94 (m, 1H), 7.10−7.17 (m, 2H), 7.21−7.25 (m, 2H) ppm.
Synthesis of 4-Bromo-N,N-diphenylaniline (1b).20 In a Schlenk
flask (250 mL), triphenylamine (6.08 g, 24.8 mmol) was dissolved in
DMF (50 mL) and cooled to 0 °C and NBS (4.41 g, 24.8 mmol
dissolved in 40 mL DMF) was added dropwise. Then, the mixture was
allowed to warm to room temperature and keep stirring overnight.
The mixture was dissolved in ethyl acetate and washed with water and
brine. The organic layer was dried over anhydrous Na2SO4 and
concentrated under a vacuum. The residue was purified by silica gel
column chromatography (petroleum ether) to afford 4-bromo-N,N-
diphenylaniline as a white solid (7.2 g, 89% yield). 1H NMR (400
MHz, CDCl3): δ = 6.95 (d, J = 8.8 Hz, 2H), 7.04 (t, J = 7.4 Hz, 2H),
7.08 (d, J = 8.0 Hz, 4H), 7.26 (t, J = 7.8 Hz, 4H), 7.33 (d, J = 8.8 Hz,
2H) ppm. 13C NMR (100 MHz, CDCl3): δ = 114.9, 123.4, 124.5,
125.3, 129.5, 132.3, 147.2, 147.5 ppm.
Synthesis of 3,4-Ethylenedioxythiophene-2-carbaldehyde (2a).21
3,4-Ethylenedioxythiophene (EDOT) (3 mL, 28 mmol) and dry DMF
(2.2 mL, 28 mmol) were stirred in dry dichloroethane (15 mL) and
cooled to 0 °C, and POCl3 (2.6 mL, 28 mmol) was added dropwise
8120
Article
over 20 min. The mixture was then allowed to warm to room
temperature and then heated to reflux for 2 h. After being cooled to
room temperature, the mixture was poured into sodium acetate
aqueous solution. After stirring for 10 min, dichloromethane was
added to the mixture. The organic layer was washed with brine, dried
over anhydrous Na2SO4, and concentrated under a vacuum. The
residue was purified by silica gel column chromatography (petroleum
ether/acetone = 6/1, V/V). 3,4-Ethylenedioxythiophene-2-carbalde-
hyde was afforded as a white solid (3.3 g, 70% yield). 1H NMR (400
MHz, CDCl3): δ = 4.26−4.28 (m, 2H), 4.35−4.37 (m, 2H), 6.80 (s,
1H), 9.90 (s, 1H) ppm. 13C NMR (100 MHz, CDCl3): δ = 64.5, 65.4,
111.0, 118.6, 141.9, 148.6, 180.3 ppm.
Synthesis of [2,2′-Bithiophene]-5-carbaldehyde (2b).22 [2,2′-
Bithiophene]-5-carbaldehyde was synthesized with a procedure similar
to that of 3,4-ethylenedioxythiophene-2-carbaldehyde, and 2,2′-
bithiophene (8.9 g, 53.3 mmol) was used as substrate to obtain
[2,2′-bithiophene]-5-carbaldehyde as a green solid (5.6 g, 54% yield).
1
H NMR (400 MHz, CDCl3): δ = 7.06−7.08 (m, 1H), 7.25 (d, J = 4.0
Hz, 1H), 7.35−7.37 (m, 2H), 7.67 (d, J = 4.0 Hz, 1H), 9.86 (s, 1H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 124.4, 126.3, 127.2, 128.5,
136.1, 137.6, 141.7, 147.3, 182.7 ppm.
Synthesis of 9-Thiophen-2-yl-9H-carbazole (2c).23 In a Schlenk
flask (250 mL), a mixture of 9H-carbazole (5.0 g, 30 mmol), 2-bromo-
thiophene (7.3 g, 45 mmol), CuI (450 mg, 2.4 mmol), KI (7.5 g, 45
mmol), K2CO3 (24.9 g, 90 mmol), and L-proline (350 mg, 3.1 mmol)
was dissolved in DMF (150 mL), heated to reflux, and kept strring for
48 h under a nitrogen atmosphere. After being cooled to room
temperature, the mixture was dissolved in dichloromethane and
washed with water and brine. The organic layer was dried over
anhydrous Na2SO4 and concentrated under a vacuum. The residue was
purified by silica gel column chromatography (petroleum ether) to
afford 2c as a white powder (4.8 g, 65% yield). 1H NMR (400 MHz,
CDCl3): δ = 7.18−7.22 (m, 2H), 7.30−7.34 (m, 2H), 7.38−7.40 (m,
1H), 7.42−7.48 (m, 4H), 8.12 (d, J = 7.6 Hz, 2H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 110.3, 120.3, 120.7, 123.6, 124.4, 125.0,
126.3, 126.4, 138.9, 142.1 ppm.
Synthesis of 9-(3,4-Ethylenedioxythiophen-2-yl)-9H-carbazole
(2d).24,25 In a Schlenk flask (250 mL), EDOT (10 g, 7.52 mL) was
dissolved in a solution of THF/HOAc (90 mL/90 mL) and cooled to
0 °C. Then, NBS (12.5 g dissolved in THF) was added dropwise. The
mixture was allowed to warm to room temperature and keep stirring
for 2 h. The mixture was dissolved in ethyl acetate and washed with
water and brine. The organic layer was dried over anhydrous Na2SO4
and concentrated under a vacuum. The residue was purified by silica
gel column chromatography (petroleum ether), and 2-bromo-3,4-
ethylenedioxythiophene was afforded as a pale yellow oil (14.3 g, 92%
yield).
Immediately, in a Schlenk flask (250 mL), a mixture of 2-bromo-
3,4-ethylenedioxythiophene (7.2 g, 32.3 mmol), 9H-carbazole (6 g,
35.5 mmol), CuI (6.2 g, 32.3 mmol), and K2CO3 (5.8 g, 42.2 mmol)
was dissolved in nitrobenzene (180 mL), and then, the mixture was
refluxed under nitrogen for 36 h. The nitrobenzene was removed by
distillation under a vacuum, and the residue was dissolved in 300 mL
of CHCl3. Then, 100 mL of H2O and 150 mL of saturated NH4OH
aqueous solution were added to the residue and the mixture was
stirred for 2 h. The organic layer was washed with water and brine and
dried over anhydrous Na2SO4, concentrated under a vacuum. The
residue was purified by silica gel column chromatography (petroleum
ether/ethyl acetate 10/1, V/V). After being recrystallized, 2d was
afforded as a white solid (3.2 g, 30% yield). M.p.: 132−138 °C. 1H
NMR (400 MHz, CDCl3): δ = 4.19−4.21 (m, 2H), 4.27−4.29 (m,
2H), 6.43 (s, 1H), 7.28−7.32 (m, 2H), 7.37−7.40 (m, 2H), 7.43−7.47
(m, 2H), 8.086−8.090 (m, 1H), 8.10−8.11 (m, 1H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 64.8, 65.0, 97.5, 110.5, 120.4, 120.6, 123.7,
126.2, 137.5, 140.9, 141.8 ppm. HRMS (ESI+): calcd for C18H14NO2S
[M + H]+ 308.0740, found 308.0744.
General Procedure for the Preparation of 3 by Direct C−H
Arylation. In a Schlenk tube, a mixture of 3-bromo-10-hexyl-10H-
phenothiazine (1a, 181.1 mg, 0.5 mmol, 1.0 equiv), thiophene-2-
carbaldehyde derivatives (2, 0.75 mmol, 1.5 equiv), Pd(OAc)2 (5.6
DOI: 10.1021/acs.joc.8b00915
J. Org. Chem. 2018, 83, 8114−8126
The Journal of Organic Chemistry
mg, 0.025 mmol, 0.05 equiv), PCy3·HBF4 (18.4 mg, 0.05 mmol, 0.1
equiv), K2CO3 (103.6 mg, 0.75 mmol, 1.5 equiv), PivOH (15.2 mg,
0.15 mmol, 0.3 equiv), and toluene (1.5 mL) was stirred at 110 °C
under a nitrogen atmosphere for 24 h. The reaction mixture was then
cooled to room temperature, diluted with dichloromethane, filtered
through a Celite pad, and washed with dichloromethane. The
combined filtrate was concentrated, and the residue was purified by
column chromatography on silica gel.
5-(10-Hexyl-10H-phenothiazin-3-yl)thiophene-2-carbaldehyde
(3a).8b Purification by column chromatography on silica gel
(petroleum ether/acetone = 10/1, v/v) afforded 3a as a red oil (175
mg, 89% yield; 3.9 g, 83% yield for gram scale). 1H NMR (400 MHz,
CDCl3): δ = 0.87 (t, J = 6.6 Hz, 3H), 1.30−1.32 (m, 4H), 1.40−1.48
(m, 2H), 1.78−1.85 (m, 2H), 3.86 (t, J = 7.2 Hz, 2H), 6.86 (t, J = 7.8
Hz, 2H), 6.94 (t, J = 7.6 Hz, 1H), 7.15 (dd, J = 7.6 Hz, 16.8 Hz, 2H),
7.28 (d, J = 4.0 Hz, 1H), 7.40−7.45 (m, 2H), 7.70 (d, J = 4.0 Hz, 1H),
9.85 (s, 1H) ppm. 13C NMR (100 MHz, CDCl3): δ = 14.1, 22.7, 26.7,
26.9, 31.6, 47.8, 115.6, 115.7, 123.0, 123.2, 123.9, 125.0, 125.68,
125.72, 127.4, 127.62, 127.64, 137.8, 141.7, 144.5, 146.5, 153.8, 182.8
ppm.
5-(10-Hexyl-10H-phenothiazin-3-yl)-3,4-ethylenedioxythio-
phene-2-carbaldehyde (3b).8b Purification by column chromatog-
raphy on silica gel (petroleum ether/acetone = 5/1, v/v) afforded 3b
as a yellow solid (185.0 mg, 82% yield). 1H NMR (400 MHz, CDCl3):
δ = 0.87 (t, J = 6.4 Hz, 3H), 1.30−1.31 (m, 4H), 1.39−1.47 (m, 2H),
1.76−1.84 (m, 2H), 3.84 (t, J = 7.2 Hz, 2H), 4.36−4.40 (m, 4H), 6.84
(t, J = 8.6 Hz, 2H), 6.92 (t, J = 7.6 Hz, 1H), 7.10−7.16 (m, 2H), 7.52
(d, J = 8.4 Hz, 1H), 7.59 (s, 1H), 9.90 (s, 1H) ppm. 13C NMR (100
MHz, CDCl3): δ = 14.1, 22.7, 26.8, 26.9, 31.6, 47.8, 64.7, 65.3, 115.0,
115.3, 115.6, 122.9, 124.1, 125.2, 125.7, 126.1, 127.5, 127.6, 128.6,
137.2, 144.6, 145.7, 149.2, 179.6 ppm.
5′-(10-Hexyl-10H-phenothiazin-3-yl)-[2,2′-bithiophene]-5-carbal-
dehyde (3c).26 Purification by column chromatography on silica gel
(petroleum ether/acetone = 10/1, v/v) afforded 3c as a red oil (190.3
mg, 80% yield). 1H NMR (400 MHz, CDCl3): δ = 0.88 (t, J = 7.0 Hz,
3H) 1.30−1.32 (m, 4H), 1.40−1.44 (m, 2H), 1.77−1.85 (m, 2H), 3.85
(t, J = 7.2 Hz, 2H), 6.83−6.88 (m, 2H), 6.91−6.96 (m, 1H), 7.12−
7.18 (m, 3H), 7.23 (d, J = 4.0 Hz, 1H), 7.30 (d, J = 3.6 Hz, 1H), 7.35−
7.38 (m, 2H), 7.67 (d, J = 4.0 Hz, 1H), 9.85 (s, 1H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 14.2, 22.8, 26.8, 26.9, 31.6, 47.7, 115.6, 122.8,
123.4, 123.9, 124.0, 124.6, 125.0, 125.6, 127.3, 127.5, 127.6, 127.9,
134.3, 137.7, 141.4, 144.8, 145.4, 145.5, 147.5, 182.6 ppm.
N,N-Diphenyl-4-(thiophen-2-yl)aniline (3d).27 Purification by silica
gel column chromatography (petroleum ether/dichloromethane = 10/
1, V/V) afforded 3d as a white solid (83.4 mg, 51% yield). 1H NMR
(400 MHz, CDCl3): δ = 7.01−7.13 (m, 9H), 7.21−7.28 (m, 6H),
7.46−7.48 (m, 2H) ppm. 13C NMR (100 MHz, CDCl3): δ = 122.4,
123.2, 123.9, 124.1, 124.6, 126.9, 128.1, 128.7, 129.4, 144.4, 147.4,
147.6 ppm.
9-Hexyl-3-(thiophen-2-yl)-9H-carbazole (3e).27 Purification by
silica gel column chromatography (petroleum ether/dichloromethane
= 10/1, V/V) afforded 3e as a pale green oil (76.7 mg, 46% yield). 1H
NMR (400 MHz, CDCl3): δ = 0.86−0.89 (m, 3H), 1.26−1.41 (m,
6H), 1.83−1.91 (m, 2H), 4.28 (t, J = 7.4 Hz, 2H), 7.10−7.12 (m, 1H),
7.23−7.27 (m, 2H), 7.34−7.35 (m, 1H), 7.37−7.41 (m, 2H), 7.46−
7.50 (m, 1H), 7.72−7.74 (m, 1H), 8.14 (d, J = 7.6 Hz, 1H), 8.33 (s,
1H) ppm. 13C NMR (100 MHz, CDCl3): δ = 14.2, 22.7, 27.1, 29.1,
31.7, 43.3, 109.0, 109.1, 118.0, 119.1, 120.6, 122.1, 122.9, 123.4, 123.7,
124.4, 125.7, 126.0, 128.1, 140.1, 141.0, 146.0 ppm. HRMS (ESI+):
calcd for C22H23NNaS [M + Na]+ 356.1449, found 356.1452.
General Procedure for Bromination of 3. A 100 mL flask with a
magnetic stirring bar was charged with 3 (8 mmol, 1.0 equiv) and
DMF (30 mL). The solution was stirred at 0 °C, and NBS (1.56 g, 8.8
mmol, 1.1 equiv) dissolved in DMF (15 mL) was added dropwise. The
mixture was allowed to warm to room temperature and keep stirring
overnight. The mixture was extracted by ethyl acetate (60 mL × 3);
the combined organic layer was washed by water and brine,
respectively, and dried over anhydrous Na2SO4 and then concentrated
under a vacuum. The crude product was purified by column
chromatography on silica gel to afford 4.
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5-(7-Bromo-10-hexyl-10H-phenothiazin-3-yl)thiophene-2-carbal-
dehyde (4a).28 Purification by column chromatography on silica gel
(petroleum ether/acetone = 10/1, v/v) afforded 4a as a red solid (2.9
g, 78% yield). M.p.: 74 °C. 1H NMR (400 MHz, CDCl3): δ = 0.87 (t, J
= 6.4 Hz, 3H), 1.29−1.31 (m, 4H), 1.39−1.46 (m, 2H), 1.74−1.82 (m,
2H), 3.81 (t, J = 7.2 Hz, 2H), 6.70 (d, J = 8.0 Hz, 1H), 6.85 (d, J = 8.8
Hz, 1H), 7.23−7.26 (m, 2H), 7.29 (d, J = 4.0 Hz, 1H), 7.38 (brs, 1H),
7.43−7.45 (m, 1H), 7.70 (d, J = 4.0 Hz, 1H), 9.86 (s, 1H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 14.2, 22.7, 26.7, 26.8, 31.5, 47.9, 115.1,
115.8, 116.8, 123.3, 125.0, 125.1, 126.0, 126.2, 127.7, 129.8, 130.3,
137.8, 141.8, 143.7, 146.0, 153.4, 182.8 ppm.
5-(7-Bromo-10-hexyl-10H-phenothiazin-3-yl)-3,4-ethylenedioxy-
thiophene-2-carbaldehyde (4b).8b Purification by column chroma-
tography on silica gel (petroleum ether/acetone = 5/1, v/v) afforded
4b as a yellow solid (3.2 g, 75% yield). M.p.: 85 °C. 1H NMR (400
MHz, CDCl3): δ = 0.86 (t, J = 6.8 Hz, 3H), 1.27−1.29 (m, 4H), 1.36−
1.41 (m, 2H), 1.71−1.79 (m, 2H), 3.78 (t, J = 7.2 Hz, 2H), 4.35−4.39
(m, 4H), 6.67 (d, J = 8.4 Hz, 1H), 6.80 (d, J = 8.8 Hz, 1H), 7.20−7.23
(m, 2H), 7.49−7.51 (m, 1H), 7.549−7.552 (m, 1H), 9.88 (s, 1H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 14.1, 22.7, 26.6, 26.8, 31.5,
47.8, 64.7, 65.3, 115.0, 115.2, 115.5, 116.7, 124.4, 125.8, 126.2, 126.38,
126.41, 128.2, 129.8, 130.2, 137.3, 143.8, 145.3, 149.1, 179.6 ppm.
5′-(7-Bromo-10-hexyl-10H-phenothiazin-3-yl)-[2,2′-bithio-
phene]-5-carbaldehyde (4c).26 Purification by column chromatog-
raphy on silica gel (petroleum ether/acetone = 10/1, v/v) afforded 4c
as a red solid (3.0 g, 68% yield). M.p.: 77−80 °C. 1H NMR (400 MHz,
CDCl3): δ = 0.87 (t, J = 7.0 Hz, 3H), 1.28−1.31 (m, 4H), 1.38−1.46
(m, 2H), 1.74−1.81 (m, 2H), 3.80 (t, J = 7.2 Hz, 2H), 6.70 (d, J = 9.2
Hz, 1H), 6.83 (d, J = 8.4 Hz, 1H), 7.15 (d, J = 4.0 Hz, 1H), 7.22−7.26
(m, 3H), 7.30 (d, J = 4.0 Hz, 1H), 7.32 (d, J = 2.0 Hz, 1H), 7.36−7.38
(m, 1H), 7.67 (d, J = 4.0 Hz, 1H), 9.85 (s, 1H) ppm. 13C NMR (100
MHz, CDCl3): δ = 14.1, 22.7, 26.7, 26.8, 31.5, 47.8, 114.9, 115.8,
116.7, 123.5, 124.0, 124.6, 124.9, 125.2, 126.3, 127.3, 128.3, 129.8,
130.2, 134.5, 137.6, 141.5, 143.9, 145.0, 145.2, 147.4, 182.6 ppm.
General Procedure for the Preparation of 5 by Direct C−H
Arylation. In a Schlenk tube, a mixture of 4 (0.5 mmol, 1.0 equiv), 2
or 3 (0.75 mmol, 1.5 equiv), Pd(OAc)2 (5.6 mg, 0.025 mmol, 0.05
equiv), PCy3·HBF4 (18.4 mg, 0.05 mmol, 0.1 equiv), K2CO3 (103.6
mg, 0.75 mmol, 1.5 equiv), PivOH (15.2 mg, 0.15 mmol, 0.3 equiv),
and toluene (2 mL) was stirred at 110 °C under a nitrogen
atmosphere for 24 h. The reaction mixture was then cooled to room
temperature, diluted with dichloromethane, filtered through a Celite
pad, and washed with dichloromethane. The combined filtrate was
concentrated, and the residue was purified by column chromatography
on silica gel.
5-(7-(5-(4-(Diphenylamino)phenyl)thiophen-2-yl)-10-hexyl-10H-
phenothiazin-3-yl)thiophene-2-carbaldehyde (5a). Purification by
column chromatography on silica gel (petroleum ether/acetone = 10/
1, v/v) afforded 5a as a red solid (183.3 mg, 51% yield). M.p.: 92 °C.
1
H NMR (400 MHz, CDCl3): δ = 0.89 (t, J = 6.2 Hz, 3H), 1.32−1.33
(m, 4H), 1.43−1.47 (m, 2H), 1.81−1.84 (m, 2H), 3.86 (t, J = 7.2 Hz,
2H), 6.84−6.86 (m, 2H), 7.03−7.08 (m, 4H), 7.12−7.17 (m, 6H),
7.28−7.29 (m, 5H), 7.36−7.48 (m, 6H), 7.70−7.71 (m, 1H), 9.86 (s,
1H) ppm. 13C NMR (100 MHz, CDCl3): δ = 14.2, 22.8, 26.7, 26.9,
31.6, 47.9, 115.5, 115.8, 123.21, 123.25, 123.4, 123.8, 124.3, 124.4,
124.6, 124.8, 125.0, 125.1, 125.8, 126.4, 127.5, 128.4, 129.5, 129.6,
137.8, 141.6, 141.7, 143.1, 143.4, 146.0, 147.4, 147.6, 153.6, 182.8
ppm. HRMS (ESI+): calcd for C45H39N2OS3 [M + H]+ 719.2219,
found 719.2215.
5-(7-(5-(4-(Diphenylamino)phenyl)thiophen-2-yl)-10-hexyl-10H-
phenothiazin-3-yl)-3,4-ethylenedioxythiophene-2-carbaldehyde
(5b). Purification by column chromatography on silica gel (petroleum
ether/acetone = 4/1, v/v) afforded 5b as a red solid (217.6 mg, 56%
yield). M.p.: 120 °C. 1H NMR (400 MHz, CDCl3): δ = 0.88 (t, J = 7.0
Hz, 3H), 1.30−1.32 (m, 4H), 1.40−1.44 (m, 2H), 1.77−1.84 (m, 2H),
3.84 (t, J = 7.2 Hz, 2H), 4.36−4.40 (m, 4H), 6.82 (dd, J = 2.4 Hz, 8.8
Hz, 2H), 7.01−7.07 (m, 4H), 7.10−7.16 (m, 6H), 7.24−7.26 (m, 3H),
7.28 (s, 1H), 7.33−7.34 (m, 1H), 7.35−7.38 (m, 1H), 7.45−7.47 (m,
2H), 7.50−7.53 (m, 1H), 7.58 (d, J = 2.0 Hz, 1H), 9.89 (s, 1H) ppm.
13
C NMR (100 MHz, CDCl3): δ = 14.1, 22.8, 26.7, 26.9, 31.6, 47.8,
DOI: 10.1021/acs.joc.8b00915
J. Org. Chem. 2018, 83, 8114−8126
The Journal of Organic Chemistry
64.7, 65.3, 115.0, 115.3, 115.6, 123.2, 123.4, 123.8, 124.3, 124.4, 124.5,
124.6, 124.7, 125.7, 126.16, 126.19, 126.4, 128.4, 128.5, 129.4, 137.3,
141.7, 143.1, 143.6, 145.2, 147.4, 147.6, 149.2, 179.6 ppm. HRMS
(ESI+): calcd for C47H41N2O3S3 [M + H]+ 777.2274, found 777.2272.
5′-(7-(5-(4-(Diphenylamino)phenyl)thiophen-2-yl)-10-hexyl-10H-
phenothiazin-3-yl)-[2,2′-bithiophene]-5-carbaldehyde (5c). Purifica-
tion by column chromatography on silica gel (petroleum ether/
acetone = 10/1, v/v) afforded 5c as a red solid (200.2 mg, 50% yield).
M.p.: 126 °C. 1H NMR (400 MHz, CDCl3): δ = 0.89 (t, J = 6.8 Hz,
3H), 1.32−1.34 (m, 4H), 1.43−1.47 (m, 2H), 1.79−1.86 (m, 2H),
3.85 (t, J = 7.2 Hz, 2H), 6.83 (d, J = 8.0 Hz, 2H), 7.02−7.08 (m, 4H),
7.12−7.16 (m, 7H), 7.23−7.25 (m, 2H), 7.29−7.31 (m, 4H), 7.35−
7.40 (m, 4H), 7.47 (d, J = 8.8 Hz, 2H), 7.66 (d, J = 3.6 Hz, 1H), 9.85
(s, 1H) ppm. 13C NMR (100 MHz, CDCl3): δ = 14.2, 22.8, 26.8, 26.9,
31.6, 47.8, 115.55, 115.65, 123.2, 123.38, 123.43, 123.8, 124.0, 124.3,
124.5, 124.57, 124.64, 124.8, 124.9, 125.1, 126.4, 127.3, 128.0, 128.4,
129.38, 129.45, 134.4, 137.6, 141.4, 141.7, 143.0, 143.8, 144.9, 145.4,
147.35, 147.43, 147.6, 182.6 ppm. HRMS (ESI+): calcd for
C49H41N2OS4 [M + H]+ 801.2096, found 801.2096.
5-(7-(5-(9H-Carbazol-9-yl)thiophen-2-yl)-10-hexyl-10H-pheno-
thiazin-3-yl)thiophene-2-carbaldehyde (5d). Purification by column
chromatography on silica gel (petroleum ether/acetone = 6/1, v/v)
afforded 5d as a yellow solid (237.1 mg, 74% yield). M.p.: 90−94 °C.
1
H NMR (400 MHz, CDCl3): δ = 0.88−0.89 (m, 3H), 1.33−1.34 (m,
4H), 1.43−1.51 (m, 2H), 1.80−1.87 (m, 2H), 3.88 (t, J = 7.2 Hz, 2H),
6.86−6.89 (m, 2H), 7.15 (d, J = 3.6 Hz, 1H), 7.25 (s, 1H), 7.28−7.34
(m, 3H), 7.39−7.47 (m, 6H), 7.54 (d, J = 8.0 Hz, 2H), 7.70 (d, J = 4.0
Hz, 1H), 8.10−8.12 (m, 2H), 9.86 (s, 1H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 14.1, 22.7, 26.7, 26.9, 31.6, 47.9, 110.2, 110.4, 115.6,
115.8, 120.4, 120.8, 121.2, 123.2, 123.7, 124.58, 124.60, 124.9, 125.1,
125.9, 126.0, 126.4, 127.6, 129.2, 137.3, 137.7, 141.6, 141.8, 142.0,
144.0, 145.9, 153.5, 182.7 ppm. HRMS (ESI + ): calcd for
C39H33N2OS3[M + H]+ 641.1750, found 641.1746.
5-(7-(5-(9H-Carbazol-9-yl)thiophen-2-yl)-10-hexyl-10H-pheno-
thiazin-3-yl)-3,4-ethylenedioxythiophene-2-carbaldehyde (5e). Pu-
rification by column chromatography on silica gel (petroleum ether/
acetone = 3/1, v/v) afforded 5e as a red solid (192.2 mg, 55% yield).
M.p.: 159−164 °C. 1H NMR (400 MHz, CDCl3): δ = 0.87−0.91 (m,
3H), 1.31−1.34 (m, 4H), 1.42−1.47 (m, 2H), 1.79−1.87 (m, 2H),
3.87 (t, J = 7.2 Hz, 2H), 4.38−4.42 (m, 4H), 6.85−6.88 (m, 2H), 7.15
(d, J = 4.0 Hz, 1H), 7.24−7.25 (m, 1H), 7.30−7.33 (m, 2H), 7.39−
7.47 (m, 4H), 7.52−7.55 (m, 3H), 7.61 (d, J = 2.0 Hz, 1H), 8.11 (d, J
= 7.6 Hz, 2H), 9.90 (s, 1H) ppm. 13C NMR (100 MHz, CDCl3): δ =
14.1, 22.8, 26.7, 26.9, 31.6, 47.9, 64.7, 65.3, 110.4, 115.1, 115.4, 115.7,
120.4, 120.8, 121.1, 123.6, 124.4, 124.6, 124.7, 125.0, 125.8, 126.0,
126.2, 126.3, 126.4, 128.3, 129.0, 137.2, 137.3, 141.7, 142.0, 144.1,
145.1, 149.2, 179.6 ppm. HRMS (ESI+): calcd for C41H35N2O3S3 [M +
H]+ 699.1804, found 699.1807.
5′-(7-(5-(9H-Carbazol-9-yl)thiophen-2-yl)-10-hexyl-10H-pheno-
thiazin-3-yl)-[2,2′-bithiophene]-5-carbaldehyde (5f). Purification by
column chromatography on silica gel (petroleum ether/acetone = 10/
1, v/v) afforded 5f as a red solid (213.3 mg, 59% yield). M.p.: 179−
182 °C. 1H NMR (400 MHz, CDCl3): δ = 0.90 (t, J = 7.0 Hz, 3H),
1.33−1.34 (m, 4H), 1.43−1.46 (m, 2H), 1.80−1.87 (m, 2H), 3.87 (t, J
= 7.0 Hz, 2H), 6.84−6.88 (m, 2H), 7.15 (t, J = 3.4 Hz, 2H), 7.23 (d, J
= 4.0 Hz, 1H), 7.25−7.26 (m, 1H), 7.30−7.48 (m, 9H), 7.53−7.55 (m,
2H), 7.66 (d, J = 4.0 Hz, 1H), 8.11 (d, J = 7.6 Hz, 2H), 9.85 (s, 1H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 14.2, 22.8, 26.7, 26.9, 31.6,
47.9, 110.4, 115.6, 115.7, 120.4, 120.8, 121.1, 123.5, 123.6, 124.0,
124.56, 124.59, 124.7, 124.8, 125.07, 125.12, 126.0, 126.4, 127.3,
128.2, 128.9, 134.4, 137.2, 137.6, 141.5, 141.7, 142.0, 144.3, 144.8,
145.3, 147.4, 182.6 ppm. HRMS (ESI+): calcd for C43H35N2OS4 [M +
H]+ 723.1627, found 723.1619.
5-(7-(5-(9H-Carbazol-9-yl)-3,4-ethylenedioxythiophen-2-yl)-10-
hexyl-10H-phenothiazin-3-yl)thiophene-2-carbaldehyde (5g). Puri-
fication by column chromatography on silica gel (petroleum ether/
acetone = 5/1, v/v) afforded 5g as a yellow solid (262.1 mg, 75%
yield). M.p.: 147 °C. 1H NMR (400 MHz, CDCl3): δ = 0.89 (t, J = 7.0
Hz, 3H), 1.31−1.34 (m, 4H), 1.42−1.49 (m, 2H), 1.79−1.87 (m, 2H),
3.86 (t, J = 7.2 Hz, 2H), 4.24−4.26 (m, 2H), 4.38−4.40 (m, 2H),
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6.84−6.87 (m, 2H), 7.27−7.32 (m, 3H), 7.40−7.47 (m, 6H), 7.50 (dd,
J = 2.0 Hz, 10.8 Hz, 1H), 7.58 (d, J = 2.4 Hz, 1H), 7.69 (d, J = 4.0 Hz,
1H), 8.09−8.11 (m, 2H), 9.85 (s, 1H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 14.1, 22.8, 26.7, 26.8, 31.6, 47.9, 64.8, 65.0, 110.5, 110.6,
114.2, 115.5, 115.6, 120.4, 120.7, 123.2, 123.8, 124.1, 125.07, 125.08,
125.2, 125.4, 125.8, 126.3, 127.5, 127.6, 136.9, 137.78, 137.85, 141.7,
143.0, 146.0, 153.7, 182.8 ppm. HRMS (ESI + ): calcd for
C41H35N2O3S3 [M + H]+ 699.1804, found 699.1806.
5-(7-(5-(9H-Carbazol-9-yl)-3,4-ethylenedioxythiophen-2-yl)-10-
hexyl-10H-phenothiazin-3-yl)-3,4-ethylenedioxythiophene-2-car-
baldehyde (5h). Purification by column chromatography on silica gel
(petroleum ether/acetone = 3/1, v/v) afforded 5h as a red solid (200.6
mg, 53% yield). M.p.: >200 °C. 1H NMR (400 MHz, CDCl3): δ =
0.89 (t, J = 6.4 Hz, 3H), 1.32−1.34 (m, 4H), 1.43−1.45 (m, 2H),
1.81−1.84 (m, 2H), 3.85 (t, J = 7.0 Hz, 2H), 4.24−4.25 (m, 2H),
4.37−4.38 (m, 6H), 6.83−6.86 (m, 2H), 7.28−7.32 (m, 2H), 7.42−
7.57 (m, 8H), 8.10 (d, J = 7.6 Hz, 2H), 9.90 (s, 1H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 14.1, 22.8, 26.7, 26.8, 31.6, 47.8, 64.6, 64.8,
65.0, 65.3, 110.4, 110.6, 114.3, 115.0, 115.2, 115.5, 120.4, 120.7, 123.8,
124.3, 124.5, 125.1, 125.3, 125.7, 126.1, 126.2, 126.3, 127.5, 128.4,
136.8, 137.3, 137.8, 141.7, 143.1, 145.3, 149.2, 179.6 ppm. HRMS
(ESI+): calcd for C43H37N2O5S3 [M + H]+ 757.1859, found 757.1860.
5-(10-Hexyl-7-(5-(9-hexyl-9H-carbazol-3-yl)thiophen-2-yl)-10H-
phenothiazin-3-yl)thiophene-2-carbaldehyde (5i). Purification by
column chromatography on silica gel (petroleum ether/dichloro-
methane = 1/1, v/v) afforded 5i as a red solid (217.5 mg, 60% yield).
M.p.: 87−92 °C. 1H NMR (400 MHz, CDCl3): δ = 0.85−0.91 (m,
6H), 1.29−1.43 (m, 12H), 1.80−1.92 (m, 4H), 3.87 (t, J = 7.2 Hz,
2H), 4.30 (t, J = 7.4 Hz, 2H), 6.84−6.87 (m, 2H), 7.21 (d, J = 3.6 Hz,
1H), 7.28−7.30 (m, 2H), 7.39−7.51 (m, 8H), 7.69 (d, J = 4.0 Hz,
1H), 7.73 (dd, J = 2.0 Hz, 8.8 Hz, 1H), 8.14 (d, J = 7.6 Hz, 1H), 8.32
(d, J = 1.6 Hz, 1H), 9.86 (s, 1H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 14.17, 14.18, 22.7, 22.8, 26.7, 26.9, 27.1, 29.1, 31.6, 31.7, 43.4, 47.9,
109.0, 109.1, 115.5, 115.8, 117.6, 119.2, 120.6, 122.9, 123.0, 123.2,
123.4, 123.5, 124.0, 124.29, 124.33, 124.8, 125.0, 125.1, 125.6, 125.8,
126.1, 127.4, 129.8, 137.8, 140.1, 141.0, 141.1, 141.7, 143.3, 144.8,
146.0, 153.7, 182.8 ppm. HRMS (ESI+): calcd for C45H45N2OS3 [M +
H]+ 725.2689, found 725.2683.
5-(7-(3,4-Ethylenedioxythiophen-2-yl)-10-hexyl-10H-phenothia-
zin-3-yl)thiophene-2-carbaldehyde (5j). Purification by column
chromatography on silica gel (petroleum ether/acetone = 5/1, v/v)
afforded 5j as a red solid (146.7 mg, 55% yield). M.p.: 154 °C. 1H
NMR (400 MHz, CDCl3): δ = 0.86 (t, J = 7.0 Hz, 3H), 1.27−1.31 (m,
4H), 1.38−1.42 (m, 2H), 1.75−1.83 (m, 2H), 3.82 (t, J = 7.2 Hz, 2H),
4.21−4.23 (m, 2H), 4.28−4.30 (m, 2H), 6.24(s, 1H), 6.80−6.82 (m,
2H), 7.25 (d, J = 2.0 Hz, 1H), 7.37 (d, J = 2.0 Hz, 1H), 7.39−7.46 (m,
2H), 7.48 (d, J = 2.4 Hz, 1H), 7.67 (d, J = 4.0 Hz, 1H), 9.83 (s, 1H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 14.1, 22.8, 26.7, 26.8, 31.6,
47.8, 64.6, 64.9, 97.1, 115.4, 115.5, 116.4, 123.1, 123.9, 124.9. 125.0,
125.1, 125.2, 125.7, 127.3, 128.3, 137.8, 141.6, 142.3, 142.6, 146.1,
153.7, 182.8 ppm. HRMS (ESI+): calcd for C29H27NNaO3S3 [M +
Na]+ 556.1045, found 556.1046.
5-(7-(3,4-Ethylenedioxythiophen-2-yl)-10-hexyl-10H-phenothia-
zin-3-yl)-3,4-ethylenedioxythiophene-2-carbaldehyde (5k). Purifica-
tion by column chromatography on silica gel (petroleum ether/
acetone = 3/1, v/v) afforded 5k as a red solid (147.9 mg, 50% yield).
M.p.: 107 °C. 1H NMR (400 MHz, CDCl3): δ = 0.88 (t, J = 6.0 Hz,
3H), 1.30−1.32 (m, 4H), 1.42−1.44 (m, 2H), 1.76−1.84 (m, 2H),
3.83 (t, J = 7.0 Hz, 2H), 4.23−4.24 (m, 2H), 4.29−4.30 (m, 2H),
4.36−4.39 (m, 4H), 6.24 (s, 1H), 6.81 (d, J = 8.8 Hz, 2H), 7.44−7.53
(m, 3H), 7.58 (s, 1H), 9.89 (s, 1H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 14.1, 22.7, 26.7, 26.8, 31.6, 47.8, 64.60, 64.63, 64.9, 65.3,
97.0, 114.9, 115.2, 115.4, 116.5, 124.0, 124.5, 124.8, 125.1, 125.7,
126.0, 126.1, 128.2, 128.5, 137.2, 137.8, 142.3, 142.7, 145.4, 179.6
ppm. HRMS (ESI+): calcd for C31H30NO5S3 [M + H]+ 592.1281,
found 592.1280.
5-(10-Hexyl-7-(5-hexyl-3,4-ethylenedioxythiophen-2-yl)-10H-
phenothiazin-3-yl)thiophene-2-carbaldehyde (5l). Purification by
column chromatography on silica gel (petroleum ether/acetone = 5/1,
v/v) afforded 5l as a red oil (188.4 mg, 61% yield). 1H NMR (400
DOI: 10.1021/acs.joc.8b00915
J. Org. Chem. 2018, 83, 8114−8126
The Journal of Organic Chemistry
MHz, CDCl3): δ = 0.86−0.91 (m, 6H), 1.30−1.32 (m, 10H), 1.57−
1.65 (m, 4H), 1.77−1.84 (m, 2H), 2.62−2.66 (m, 2H), 3.84 (t, J = 7.2
Hz, 2H), 4.20−4.22 (m, 2H), 4.27−4.28 (m, 2H), 6.79−6.83 (m, 2H),
7.26−7.28 (m, 1H), 7.38−7.39 (m, 1H), 7.40−7.41 (m, 1H), 7.42−
7.43 (m, 1H), 7.457−7.463 (m, 1H), 7.69 (d, J = 4.0 Hz, 1H), 9.85 (s,
1H) ppm. 13C NMR (100 MHz, CDCl3): δ = 14.1, 14.2, 22.7, 25.9,
26.7, 26.9, 29.0, 30.6, 31.6, 31.7, 47.8, 64.5, 65.0, 111.9, 115.3, 115.6,
116.4, 123.1, 123.8, 124.6, 124.8, 125.0, 125.2, 125.7, 127.2, 128.7,
137.7, 137.8, 138.0, 141.6, 142.0, 146.3, 153.8, 182.7 ppm. HRMS
(ESI+): calcd for C35H40NO3S3 [M + H]+ 618.2165, found 618.2163.
General Procedure for Knö venagel Condensations of 3 or 5
with Cyanoacetic Acid. In a Schlenk tube, a mixture of 3 or 5 (0.25
mmol, 1.0 equiv) and cyanoacetic acid (64 mg, 0.75 mmol. 3.0 equiv)
was dissolved in CHCl3 (2 mL) and then piperidine (74 μL, 0.75
mmol, 3.0 equiv) was added. The mixture was heated to reflux under a
nitrogen atmosphere and kept stirring for 6 h. Then, the mixture was
cooled to room temperature and diluted by dichloromethane (20 mL).
Then, HCl (1 M, 10 mL) was added and kept stirring at room
temperature for 1 h. After separation of the CH2Cl2 layer, the aqueous
layer was extracted with CH2Cl2 (2 × 10 mL). The combined organic
phase was washed with water and brine, respectively, and dried over
Na2SO4. After removal of the solvent under reduced pressure, the
residue was purified by silica gel column chromatography to afford 6.
3-(5-(7-(5-(4-(Diphenylamino)phenyl)thiophen-2-yl)-10-hexyl-
10H-phenothiazin-3-yl)thiophen-2-yl)-2-cyanoacrylic Acid (6a).
Purification by column chromatography on silica gel (dichloro-
methane/methanol = 20/1, v/v) afforded 6a as a dark red solid
(141.5 mg, 72% yield). M.p.: >280 °C. 1H NMR (400 MHz, DMSO-
d6): δ = 0.78 (brs, 3H), 1.19 (brs, 4H), 1.33 (brs, 2H), 1.62 (brs, 2H),
3.80 (brs, 2H), 6.93−7.07 (m, 10H), 7.27−7.53 (m, 13H), 7.70 (brs,
1H), 8.16 (s, 1H) ppm. 13C NMR (100 MHz, DMSO-d6): δ = 13.8,
22.1, 25.8, 26.1, 30.8, 46.7, 116.1, 116.2, 119.0, 123.1, 123.3, 123.38,
123.43, 123.6, 123.8, 123.9, 124.0, 124.2, 124.6, 125.4, 126.2, 127.2,
127.6, 128.5, 129.6, 135.2, 136.7, 140.6, 141.4, 141.8, 143.0, 144.6,
146.7, 146.8, 148.0, 164.1 ppm. HRMS (ESI + ): calcd for
C48H40N3O2S3 [M + H]+ 786.2277, found 786.2281. Anal. Calcd for
C48H39N3O2S3 (%): C, 73.35; H, 5.00; N, 5.35; S, 12.24. Found: C,
73.28; H, 5.03; N, 5.27; S, 12.31.
3-(5-(7-(5-(4-(Diphenylamino)phenyl)thiophen-2-yl)-10-hexyl-
10H-phenothiazin-3-yl)-3,4-ethylenedioxythiophen-2-yl)-2-cyanoa-
crylic Acid (6b). Purification by column chromatography on silica gel
(dichloromethane/methanol = 20/1, v/v) afforded 6b as a dark red
solid (145.6 mg, 69% yield). M.p.: 238−245 °C. 1H NMR (400 MHz,
DMSO-d6): δ = 0.84−0.85 (m, 3H), 1.23−1.25 (m, 4H), 1.39−1.40
(m, 2H), 1.69−1.72 (m, 2H), 3.91 (brs, 2H), 4.44−4.46 (m, 4H),
6.98−7.12 (m, 10H), 7.31−7.64 (m, 12H), 8.13 (s, 1H) ppm. HRMS
(ESI+): calcd for C50H42N3O4S3 [M + H]+ 844.2332, found 844.2326.
Anal. Calcd for C50H41N3O4S3 (%): C, 71.15; H, 4.90; N, 4.98; S,
11.39. Found: C, 71.04; H, 4.91; N, 4.88; S, 11.50.
3-(5′-(7-(5-(4-(Diphenylamino)phenyl)thiophen-2-yl)-10-hexyl-
10H-phenothiazin-3-yl)-[2,2′-bithiophen]-5-yl)-2-cyanoacrylic Acid
(6c). Purification by column chromatography on silica gel (dichloro-
methane/methanol = 20/1, v/v) afforded 6c as a dark red solid (172.6
mg, 80% yield). M.p.: 266−269 °C. 1H NMR (400 MHz, DMSO-d6):
δ = 0.79 (t, J = 7.0 Hz, 3H), 1.20−1.22 (m, 4H), 1.32−1.36 (m, 2H),
1.61−1.68 (m, 2H), 3.83 (t, J = 6.0 Hz, 2H), 6.94−7.07 (m, 10H),
7.28−7.34 (m, 5H), 7.39−7.45 (m, 8H), 7.53 (d, J = 8.4 Hz, 2H), 7.69
(d, J = 4.0 Hz, 1H), 8.16 (s, 1H) ppm. 13C NMR (100 MHz, DMSO-
d6): δ = 13.9, 22.1, 25.8, 26.1, 30.8, 46.7, 69.8, 107.4, 116.0, 116.2,
118.8, 123.1, 123.4, 123.5, 123.6, 124.0, 124.2, 124.36, 124.41, 124.5,
124.9, 126.2, 127.1, 127.5, 127.6, 128.3, 129.6, 133.9, 135.3, 137.1,
140.6, 141.8, 142.0, 143.2, 143.9, 146.7, 146.8 ppm. HRMS (ESI+):
calcd for C52H42N3O2S4 [M + H]+ 868.2154, found 868.2154. Anal.
Calcd for C52H41N3O2S4 (%): C, 71.94; H, 4.76; N, 4.84; S, 14.77.
Found: C, 71.88; H, 4.78; N, 4.72; S, 14.82.
3-(5-(7-(5-(9H-Carbazol-9-yl)thiophen-2-yl)-10-hexyl-10H-pheno-
thiazin-3-yl)thiophen-2-yl)-2-cyanoacrylic Acid (6d). Purification by
column chromatography on silica gel (dichloromethane/methanol =
20/1, v/v) afforded 6d as a dark red solid (132.7 mg, 75% yield). M.p.:
266−270 °C. 1H NMR (400 MHz, DMSO-d6): δ = 0.83 (t, J = 7.0 Hz,
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3H), 1.22−1.26 (m, 4H), 1.37−1.44 (m, 2H), 1.67−1.74 (m, 2H),
3.92 (t, J = 6.8 Hz, 2H), 7.08−7.11 (m, 2H), 7.31−7.35 (m, 2H), 7.38
(d, J = 3.6 Hz, 1H), 7.46−7.54 (m, 6H), 7.57−7.60 (m, 3H), 7.68 (d, J
= 4.4 Hz, 1H), 7.94 (d, J = 4.0 Hz, 1H), 8.23 (d, J = 7.6 Hz, 2H), 8.42
(s, 1H) ppm. 13C NMR (100 MHz, DMSO-d6): δ = 13.9, 22.1, 25.8,
26.1, 30.8, 46.9, 110.2, 116.4, 116.5, 116.9, 120.6, 121.0, 122.3, 123.0,
123.5, 123.7, 123.8, 124.42, 124.44, 125.1, 126.1, 126.6, 126.8, 126.9,
128.3, 134.0, 136.0, 140.5, 141.1, 141.2, 143.4, 145.3, 163.7 pm.
HRMS (ESI+): calcd for C42H34N3O2S3 [M + H]+ 708.1808, found
708.1801. Anal. Calcd for C42H33N3O2S3 (%): C, 71.26; H, 4.70; N,
5.94; S, 13.59. Found: C, 71.21; H, 4.72; N, 5.82; S, 13.68.
3-(5-(7-(5-(9H-Carbazol-9-yl)thiophen-2-yl)-10-hexyl-10H-pheno-
thiazin-3-yl)-3,4-ethylenedioxythiophen-2-yl)-2-cyanoacrylic Acid
(6e). Purification by column chromatography on silica gel (dichloro-
methane/methanol = 20/1, v/v) afforded 6e as a dark red solid (160.8
mg, 84% yield). M.p.: 235−240 °C. 1H NMR (400 MHz, DMSO-d6):
δ = 0.82−0.85 (m, 3H), 1.22−1.27 (m, 4H), 1.37−1.42 (m, 2H),
1.68−1.73 (m, 2H), 3.91 (t, J = 6.2 Hz, 2H), 4.44−4.50 (m, 4H),
7.08−7.12 (m, 2H), 7.32−7.35 (m, 2H), 7.38−7.39 (m, 1H), 7.46−
7.60 (m, 9H), 8.18 (s, 1H), 8.24 (d, J = 8.0 Hz, 2H) ppm. 13C NMR
(100 MHz, DMSO-d6): δ = 13.9, 22.1, 25.7, 26.0, 30.8, 46.8, 64.8, 65.6,
108.2, 110.1, 112.4, 116.2, 116.4, 117.4, 120.6, 120.9, 122.2, 122.9,
123.2, 123.4, 123.7, 124.6, 125.0, 125.5, 126.2, 126.5, 126.7, 128.2,
136.0, 137.8, 140.4, 141.0, 143.4, 144.6, 164.0 ppm. HRMS (ESI+):
calcd for C44H36N3O4S3 [M + H]+ 766.1862, found 766.1856. Anal.
Calcd for C44H35N3O4S3 (%): C, 69.00; H, 4.61; N, 5.49; S, 12.56.
Found: C, 68.92; H, 4.72; N, 5.38; S, 12.63.
3-(5′-(7-(5-(9H-Carbazol-9-yl)thiophen-2-yl)-10-hexyl-10H-phe-
nothiazin-3-yl)-[2,2′-bithiophen]-5-yl)-2-cyanoacrylic Acid (6f). Pu-
rification by column chromatography on silica gel (dichloromethane/
methanol = 20/1, v/v) afforded 6f as a dark red solid (156.0 mg, 79%
yield). M.p.: 254−260 °C. 1H NMR (400 MHz, DMSO-d6): δ = 0.79
(t, J = 7.0 Hz, 3H), 1.18−1.23 (m, 4H), 1.31−1.36 (m, 2H), 1.61−
1.68 (m, 2H), 3.83 (t, J = 6.0 Hz, 2H), 6.95−7.00 (m, 2H), 7.29−7.34
(m, 3H), 7.41−7.50 (m, 11H), 7.54 (d, J = 4.0 Hz, 1H), 7.70 (d, J =
4.0 Hz, 1H), 8.18−8.22 (m, 3H) ppm. 13C NMR (100 MHz, DMSO-
d6): δ = 13.9, 22.1, 25.8, 26.1, 30.8, 46.7, 69.8, 110.1, 116.1, 116.2,
118.7, 120.6, 120.9, 122.1, 122.9, 123.63, 123.64, 124.38, 124.45,
124.9, 126.4, 126.7, 127.2, 127.5, 128.0, 133.9, 135.1, 135.8, 137.5,
140.5, 141.0, 141.8, 142.3, 143.3, 143.7, 143.9, 163.81, 163.83 ppm.
HRMS (ESI+): calcd for C46H36N3O2S4 [M + H]+ 790.1685, found
790.1691. Anal. Calcd for C46H35N3O2S4 (%): C, 69.93; H, 4.47; N,
5.32; S, 16.23. Found: C, 69.98; H, 4.49; N, 5.24; S, 16.31.
3-(5-(7-(5-(9H-Carbazol-9-yl)-3,4-ethylenedioxythiophen-2-yl)-
10-hexyl-10H-phenothiazin-3-yl)thiophen-2-yl)-2-cyanoacrylic Acid
(6g). Purification by column chromatography on silica gel (dichloro-
methane/methanol = 20/1, v/v) afforded 6g as a dark red solid (158.9
mg, 83% yield). M.p.: 225−230 °C. 1H NMR (400 MHz, DMSO-d6):
δ = 0.80 (brs, 3H), 1.22 (brs, 4H), 1.36 (brs, 2H), 1.66 (brs, 2H), 3.84
(brs, 2H), 4.29 (brs, 2H), 4.43 (brs, 2H), 7.00−7.03 (m, 2H), 7.28−
7.31 (m, 2H), 7.40−7.52 (m, 8H), 7.63 (brs, 1H), 7.93 (brs, 1H), 8.19
(d, J = 8.0 Hz, 2H), 8.43 (s, 1H) ppm. 13C NMR (100 MHz, DMSO-
d6): δ = 13.9, 22.1, 25.8, 26.1, 30.8, 46.8, 64.6, 65.0, 97.8, 108.9, 110.5,
112.6, 116.2, 116.3, 116.7, 120.5, 120.8, 122.99, 123.01, 123.6, 124.0,
124.3, 124.4, 125.2, 126.0, 126.5, 126.7, 127.0, 133.8, 137.3, 138.1,
140.9, 141.5, 142.4, 145.3, 146.5, 152.0, 163.8 ppm. HRMS (ESI+):
calcd for C44H36N3O4S3 [M + H]+ 766.1862, found 766.1870. Anal.
Calcd for C44H35N3O4S3 (%): C, 69.00; H, 4.61; N, 5.49; S, 12.56.
Found: C, 68.95; H, 4.66; N, 5.44; S, 12.67.
3-(5-(7-(5-(9H-Carbazol-9-yl)-3,4-ethylenedioxythiophen-2-yl)-
10-hexyl-10H-phenothiazin-3-yl)-3,4-ethylenedioxythiophen-2-yl)-
2-cyanoacrylic Acid (6h). Purification by column chromatography on
silica gel (dichloromethane/methanol = 20/1, v/v) afforded 6h as a
dark red solid (166.8 mg, 81% yield). M.p.: 195−200 °C. 1H NMR
(400 MHz, DMSO-d6): δ = 0.82 (t, J = 7.2 Hz, 3H), 1.23−1.26 (m,
4H), 1.34−1.41 (m, 2H), 1.64−1.71 (m, 2H), 3.86 (t, J = 7.0 Hz, 2H),
4.29−4.30 (m, 2H), 4.43−4.48 (m, 6H), 7.05 (d, J = 8.8 Hz, 2H),
7.28−7.32 (m, 2H), 7.42−7.54 (m, 8H), 8.17−8.21 (m, 3H) ppm. 13C
NMR (100 MHz, DMSO-d6): δ = 13.9, 22.2, 25.8, 26.1, 30.9, 46.8,
64.6, 64.8, 65.0, 65.7, 108.2, 108.9, 110.5, 112.6, 116.0, 116.3, 117.3,
DOI: 10.1021/acs.joc.8b00915
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The Journal of Organic Chemistry
120.5, 120.8, 122.9, 123.0, 123.1, 124.0, 124.6, 125.2, 125.8, 126.6,
127.0, 137.3, 137.8, 138.1, 140.9, 142.4, 144.7, 149.3, 164.2 ppm.
HRMS (ESI+): calcd for C46H38N3O6S3 [M + H]+ 824.1917, found
824.1908. Anal. Calcd for C46H37N3O6S3 (%): C, 67.05; H, 4.53; N,
5.10; S, 11.67. Found: C, 66.98; H, 4.62; N, 5.03; S, 11.78.
3-(5-(10-Hexyl-7-(5-(9-hexyl-9H-carbazol-3-yl)thiophen-2-yl)-
10H-phenothiazin-3-yl)thiophen-2-yl)-2-cyanoacrylic Acid (6i). Pu-
rification by column chromatography on silica gel (dichloromethane/
methanol = 10/1, v/v) afforded 6i as a dark red solid (162.6 mg, 82%
yield). M.p.: 167−175 °C. 1H NMR (400 MHz, DMSO-d6): δ =
0.77−0.82 (m, 6H), 1.18−1.38 (m, 12H), 1.67−1.76 (m, 4H), 3.87−
3.90 (m, 2H), 4.36−4.39 (m, 2H), 7.03−7.06 (m, 1H), 7.20−7.24 (m,
1H), 7.45−7.49 (m, 4H), 7.54−7.67 (m, 5H), 7.72−8.05 (m, 4H),
8.22−8.26 (m, 1H), 8.35−8.38 (m, 1H), 8.42−8.52 (m, 1H) ppm.
HRMS (ESI+): calcd for C48H45N3NaO2S3 [M + Na]+ 814.2566,
found 814.2572. Anal. Calcd for C48H45N3O2S3 (%): C, 72.79; H,
5.73; N, 5.31; S, 12.14. Found: C, 72.68; H, 5.80; N, 5.25; S, 12.23.
3-(5-(7-(3,4-Ethylenedioxythiophen-2-yl)-10-hexyl-10H-pheno-
thiazin-3-yl)thiophen-2-yl)-2-cyanoacrylic Acid (6j). Purification by
column chromatography on silica gel (dichloromethane/methanol =
20/1, v/v) afforded 6j as a dark red solid (118.6 mg, 79% yield). M.p.:
>280 °C. 1H NMR (400 MHz, DMSO-d6): δ = 0.79−0.82 (m, 3H),
1.22−1.23 (m, 4H), 1.35−1.36 (m, 2H), 1.64−1.68 (m, 2H), 3.85
(brs, 2H), 4.23−4.31 (m, 4H), 6.55 (s, 1H), 7.00−7.02 (m, 2H),
7.40−7.42 (m, 2H), 7.50−7.52 (m, 2H), 7.59−7.60 (m, 1H), 7.80−
7.81 (m, 1H), 8.26 (s, 1H) ppm. 13C NMR (100 MHz, DMSO-d6): δ
= 13.9, 22.1, 25.8, 26.1, 30.9, 46.7, 64.2, 64.8, 97.4, 114.8, 116.1, 116.2,
118.2, 122.9, 123.6, 123.7, 124.0, 124.2, 124.8, 125.7, 127.0, 127.7,
134.7, 138.0, 138.7, 142.1, 142.2, 143.3, 145.0, 149.5, 163.9 ppm.
HRMS (ESI+): calcd for C32H29N2O4S3 [M + H]+ 601.1284, found
601.1296. Anal. Calcd for C32H28N2O4S3 (%): C, 63.98; H, 4.70; N,
4.66; S, 16.01. Found: C, 63.89; H, 4.77; N, 4.54; S, 16.23.
3-(5-(7-(3,4-Ethylenedioxythiophen-2-yl)-10-hexyl-10H-pheno-
thiazin-3-yl)-3,4-ethylenedioxythiophen-2-yl)-2-cyanoacrylic Acid
(6k). Purification by column chromatography on silica gel (dichloro-
methane/methanol = 20/1, v/v) afforded 6k as a dark red solid (128.5
mg, 78% yield). M.p.: 252−254 °C. 1H NMR (400 MHz, DMSO-d6):
δ = 0.81 (t, J = 6.6 Hz, 3H), 1.22−1.23 (m, 4H), 1.34−1.35 (m, 2H),
1.64−1.67 (m, 2H), 3.82 (brs, 2H), 4.226−4.234 (m, 2H), 4.30−4.31
(m, 2H), 4.42−4.45 (m, 4H), 6.55 (s, 1H), 7.00 (t, J = 8.4 Hz, 2H),
7.39−7.42 (m, 2H), 7.47−7.50 (m, 2H), 8.15 (s, 1H) ppm. 13C NMR
(100 MHz, DMSO-d6): δ = 13.9, 22.1, 25.8, 26.0, 30.8, 46.7, 64.2, 64.8,
65.4, 69.8, 97.4, 108.5, 114.8, 115.9, 116.1, 118.3, 122.8, 123.1, 123.5,
124.4, 124.7, 125.6, 125.9, 127.7, 137.6, 138.0, 142.0, 142.2, 144.4,
147.8 ppm. HRMS (ESI+): calcd for C34H30N2NaO6S3 [M + Na]+
681.1158, found 681.1158. Anal. Calcd for C34H30N2O6S3 (%): C,
61.99; H, 4.59; N, 4.25; S, 14.60. Found: C, 61.89; H, 4.58; N, 4.13; S,
14.69.
3-(5-(10-Hexyl-7-(5-hexyl-3,4-ethylenedioxythiophen-2-yl)-10H-
phenothiazin-3-yl)thiophen-2-yl)-2-cyanoacrylic Acid (6l). Purifica-
tion by column chromatography on silica gel (dichloromethane/
methanol = 20/1, v/v) afforded 6l as a dark red solid (137.0 mg, 80%
yield). 1H NMR (400 MHz, DMSO-d6): δ = 0.79−0.86 (m, 6H),
1.21−1.30 (m, 12H), 1.48−1.52 (m, 2H), 1.63−1.68 (m, 2H), 2.57 (t,
J = 7.6 Hz, 2H), 3.85 (t, J = 6.6 Hz, 2H), 4.21−4.29 (m, 4H), 6.98−
7.04 (m, 2H), 7.35−7.37 (m, 2H), 7.51−7.55 (m, 2H), 7.64 (d, J = 4.0
Hz, 1H), 7.92 (d, J = 4.4 Hz, 1H), 8.39 (s, 1H) ppm. 13C NMR (100
MHz, DMSO-d6): δ = 13.9, 14.0, 22.09, 22.12, 25.2, 25.8, 26.1, 28.2,
29.9, 30.8, 31.0, 46.7, 64.2, 64.9, 110.6, 114.96, 114.97, 116.1, 116.2,
117.0, 122.8, 123.3, 123.7, 124.2, 126.7, 128.0, 134.0, 137.9, 138.2,
141.5, 145.4, 151.5, 163.8 ppm. HRMS (ESI + ): calcd for
C38H41N2O4S3 [M + H]+ 685.2223, found 685.2225. Anal. Calcd for
C38H40N2O4S3 (%): C, 66.64; H, 5.89; N, 4.09; S, 14.04. Found: C,
66.52; H, 5.99; N, 4.01; S, 13.98.
3-(5-(10-Hexyl-10H-phenothiazin-3-yl)thiophen-2-yl)-2-cyanoa-
crylic Acid (6m).15 Purification by column chromatography on silica
gel (dichloromethane/methanol = 20/1, v/v) afforded 6m as a dark
red solid (93.3 mg, 81% yield). M.p.: 160−165 °C. 1H NMR (400
MHz, DMSO-d6): δ = 0.81 (brs, 3H), 1.23 (brs, 4H), 1.37 (brs, 2H),
1.66 (brs, 2H), 3.87 (brs, 2H), 6.96−7.21 (m, 5H), 7.55 (brs, 2H),
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7.68 (brs, 1H), 7.96 (brs, 1H), 8.46 (s, 1H) ppm. 13C NMR (100
MHz, DMSO-d6): δ = 13.9, 22.1, 25.8, 26.1, 30.8, 46.7, 97.8, 116.1,
116.2, 116.7, 122.5, 123.0, 124.28, 124.34, 124.4, 125.9, 126.6, 127.2,
127.9, 133.8, 141.6, 143.8, 145.8, 146.5, 152.1, 163.8 ppm. HRMS
(ESI+): calcd for C26H25N2O2S2 [M + H]+ 461.1352, found 461.1357.
Anal. Calcd for C26H24N2O2S2 (%): C, 67.80; H, 5.25; N, 6.08; S,
13.92. Found: C, 67.69; H, 5.35; N, 5.99; S, 14.04.
3-(5′-(10-Hexyl-10H-phenothiazin-3-yl)-[2,2′-bithiophen]-5-yl)-2-
cyanoacrylic Acid (6n). Purification by column chromatography on
silica gel (dichloromethane/methanol = 20/1, v/v) afforded 6n as a
dark red solid (103.1 mg, 76% yield). M.p.: 200−212 °C. 1H NMR
(400 MHz, DMSO-d6): δ = 0.81 (t, J = 7.0 Hz, 3H), 1.22−1.25 (m,
4H), 1.35−1.39 (m, 2H), 1.63−1.68 (m, 2H), 3.86 (t, J = 7.0 Hz, 2H),
6.93−6.97 (m, 1H), 7.00−7.02 (m, 2H), 7.14−7.16 (m, 1H), 7.18−
7.22 (m, 1H), 7.47−7.51 (m, 3H), 7.54 (d, J = 4.0 Hz, 1H), 7.57−7.58
(m, 1H), 7.94 (d, J = 4.4 Hz, 1H), 8.45 (s, 1H) ppm. 13C NMR (100
MHz, DMSO-d6): δ = 13.9, 22.1, 25.8, 26.2, 30.8, 46.6, 116.0, 116.1,
116.8, 122.8, 123.7, 124.4, 124.6, 124.8, 125.0, 127.18, 127.23, 127.8,
128.3, 133.3, 133.8, 144.1, 144.5, 144.8, 145.6, 163.7 ppm. HRMS
(ESI+): calcd for C30H27N2O2S3 [M + H]+ 543.1229, found 543.1221.
Anal. Calcd for C30H26N2O2S3 (%): C, 66.39; H, 4.83; N, 5.16; S,
17.72. Found: C, 66.30; H, 4.88; N, 5.05; S, 17.64.
Measurement of CV Curves. In consideration of the solubility of
dyes, we used DMSO instead of DCM as solvent for measurement of
CV curves. Cyclic voltammetry (CV) was measured in DMSO with 0.1
M tetra-n-butylammonium hexafluorophosphate (TBAPF6) as a
supporting electrolyte (scanning rate, 50 mV s−1; counter electrode,
a platinum wire; working electrode, a platinum plate; reference
electrode, Ag/Ag+ (0.01 M AgNO3 in acetonitrile)) and ferrocene/
ferricenium (Fc+/Fc) as an external standard at 0.63 V (vs NHE).29
The value of the ground oxidation potential was calculated according
to Eox (vs NHE) = Eox + 0.63 V.
Fabrication of DSSC Devices. Dyes 6a−6n (0.01 mmol) were
dissolved in a mixture of CH2Cl2/THF (9/1, 20 mL) and kept stirring
for 1 h at room temperature. After fitration of the mixture by a
microporous filtering film, the TiO2 photoanode (0.4 cm × 0.4 cm)
was immersed in the dye solution for 12 h and then rinsed with
CH2Cl2/THF (9/1) and dried by air flow. The TiO2 photoanode was
clipped onto the Pt-counter electrode with a small gap caused by a 30
μm parafilm (Sigma-Aldrich) between these two electrodes. The I−/
I3− electrolyte (1.0 M DMPII, 0.1 M LiI, 0.05 M I2, 0.5 M TBP in
CH3CN) was then syringed into the gap between these two electrodes.
■ ASSOCIATED CONTENT
* Supporting Information
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.joc.8b00915.
Cyclic voltammograms of organic dyes (6a−6n),
optimization of DSSC fabrication, and copies of 1H
NMR and 13C NMR spectra of key intermediates and
final products (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: rl.wang@scu.edu.cn.
*E-mail: jingbolan@scu.edu.cn.
ORCID
Jingbo Lan: 0000-0001-5937-0987
Jingsong You: 0000-0002-0493-2388
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by grants from the National NSF of
China (Nos. 21672154, 21432005, and 21772133) and
DOI: 10.1021/acs.joc.8b00915
J. Org. Chem. 2018, 83, 8114−8126
The Journal of Organic Chemistry
Comprehensive Training Platform of Specialized Laboratory,
College of Chemistry, Sichuan University.
■
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8126 DOI: 10.1021/acs.joc.8b00915

J. Org. Chem. 2018, 83, 8114−8126