268
Y.-Z. Lin et al. / Tetrahedron 70 (2014) 262e269
þ
2
7.8, 23.3, 14.1, 14.0. MS (EI, 70 eV): m/z (relative intensity) 611 (M ,
106.3, 104.3, 104.0, 67.7, 67.5, 67.3, 67.2, 30.7, 30.4, 30.3, 30.2, 30.1,
100); HRMS calcd for C40
H38NBr: 611.2188, found 611.2188.
25.7, 25.6, 25.4, 25.3, 25.1, 19.6, 19.5, 12.7, 12.6. MS (FAB, 70 eV): m/z
þ
(relative intensity) 958 (M , 100); HRMS calcd for C62
H
66
N
2
O
2
SSi
2
:
4.1.6. 5-(2-(4-(Diphenylamino)phenyl)-9,10-bis(2-(triisopropyl-silyl)
958.4384, found 958.4408.
ethynyl)anthracen-6-yl)thiophene-2-carbaldehyde (6a). A mixture
of 4a (500 mg, 0.6 mmol), (5-(1,3-dioxolan-2-y-l)thiophen-2-yl)
4.1.9. (E)-3-(5-(2-(4-(Diphenylamino)phenyl)-9,10-dibutyl-an-
thracen-6-yl)thiophen-2-yl)-2-cyanoacrylic acid (AN-Bu). Compound
AN-Bu was synthesized according to the same procedure as that of
tributylstannane (517 mg, 1.2 mmol), PdCl
2
(PPh
3
)
2
(20.4 mg,
ꢂ
0
.03 mmol) were dissolved in dry DMF, then heated to 90 C with
stirring. After 24 h, the reaction was cooled to room temperature,
then quenched by the addition of methanol and saturated KF(aq)
AN-TIPS. Dark red solid of AN-Bu was obtained in 70% yield; mp
ꢂ
159e161 C; IR (KBr)
nmax 3526, 2955, 2852, 1692, 1683, 1498, 1413,
ꢀ
1 1
(
15 mL). The mixture was extracted with CH
2
Cl
2
, while the organic
1315 cm ; H NMR (400 MHz, CDCl
3
): 8.47 (s, 1H), 8.45 (s, 1H),
d
layer was dried over anhydrous MgSO . Evaporation of the solvent
4
8.44 (d, 1H, J¼2.0 Hz), 8.42 (d, 1H, J¼2.1 Hz), 8.40 (s, 1H), 7.94 (d, 1H,
J¼4.0 Hz), 7.88 (d, 1H, J¼9.2 Hz), 7.85 (d, 1H, J¼9.2 Hz), 7.78 (d, 1H,
J¼3.9 Hz), 7.74 (d, 2H, J¼8.4 Hz), 7.28 (t, 4H, J¼7.7 Hz), 7.18 (d, 2H,
J¼8.4 Hz), 7.13 (d, 4H, J¼7.9 Hz), 7.03 (t, 2H, J¼7.7 Hz), 3.68e3.76 (m,
4H), 1.81e1.88 (m, 4H), 1.60e1.68 (m, 4H), 1.10 (t, 3H, J¼7.3 Hz), 1.04
gave a crude product. The crude mixture was added Acetic acid/
ꢂ
THF/de-ionized water (40/20/10 mL) at 90 C. After 3 h, the re-
action was quenched by adding de-ionized water and brine. To
mixture extracted with CH
over anhydrous MgSO and evaporated under vacuum, which was
purified by silica gel column chromatograph eluted by CH Cl
hexane (1/4). Red solid of 6a was obtained in 55% yield (285 mg,
2 2
Cl , and the organic layer was dried
13
4
(t, 3H, J¼7.3 Hz); C NMR (100 MHz, CDCl
3
): d 164.4, 148.8, 148.7,
2
2
/
146.3, 139.9, 138.2, 136.6, 136.0, 135.9, 135.1, 131.6, 130.6, 130.4, 130.3,
130.2, 130.1, 128.8, 127.5, 127.0, 126.0, 125.7, 125.5, 124.8, 124.1, 123.8,
ꢂ
1
0
1
2
.3 mmol); mp 165e167 C; H NMR (400 MHz, CDCl
3
):
d
9.94 (s,
122.7, 116.9, 34.9, 34.8, 28.6, 28.5, 14.7, 14.6; MS (FAB, 70 eV): m/z
þ
H), 9.00 (s, 1H), 8.85 (s, 1H), 8.66 (d, 2H, J¼8.9 Hz), 7.86e7.93 (m,
(relative intensity) 710 ((MþH) , 100); HRMS calcd for C48
43 2 2
H N O S:
H), 7.81 (d, 1H, J¼3.9 Hz), 7.70 (d, 2H, J¼8.5 Hz), 7.61 (d, 1H,
710.2967, found 710.2991.
J¼3.8 Hz), 7.30 (t, 4H, J¼7.8 Hz), 7.17e7.20 (m, 6H), 7.0 (t, 2H,
1
3
J¼7.3 Hz), 1.2e1.3 (m, 42H); C NMR (100 MHz, CDCl
54.0, 147.8, 147.5, 142.8, 139.0, 137.3, 133.9, 133.3, 132.4, 132.1, 131.9,
30.9, 129.3, 128.4, 128.0, 127.8, 126.9, 124.9, 124.6, 123.9, 123.6,
3
):
d
182.5,
4.2. Fabrication of DSSCs and characterization of DSSCs
1
1
The FTO conducting glass (FTO glass, fluorine doped tin oxide
1
7
C
23.1, 119.1, 118.6, 105.9, 105.52, 103.0, 102.8, 18.9, 11.5; MS (FAB,
over-layer, transmission >90% in the visible, sheet resistance
þ
ꢀ1
0 eV): m/z (relative intensity) 892 ((MþH) , 100); HRMS calcd for
8
U
square ), titania-oxide pastes of Ti-Nanoxide T/SP and Ti-
59
H
66NOSSi
2
:892.4404, found 892.4438.
Nanoxide R/SP were purchased from Solaronix. A thin film of TiO
2
2
(16e18
mm thick) was coated on a 0.25 cm FTO glass substrate,
4
.1.7. 5-(2-(4-(Diphenylamino)phenyl)-9,10-dibutylanthracen-6-yl)
while the thickness was measured by Veeco Dektak 150. It was
ꢀ
4
thiophene-2-carbaldehyde (6b). Compound 6b was synthesized
according to the same procedure as that of 6a. Light yellow solid of
immersed in a THF solution containing 3ꢁ10 M dye sensitizers
for at least 12 h, then rinsed with anhydrous acetonitrile and dried.
Another piece of FTO with sputtering 100 nm thick Pt was used as
ꢂ
1
6
b was obtained in 51% yield; mp 145e147 C; H NMR (400 MHz,
CDCl ):
9.93 (s, 1H), 8.63 (d, 1H, J¼1.6 Hz), 8.44 (d, 1H, J¼1.3 Hz),
.36 (d, 1H, J¼9.2 Hz), 8.35 (d, 1H, J¼9.2 Hz), 7.78e7.82 (m, 2H), 7.76
dd, 1H, J¼9.3, 1.3 Hz), 7.67 (d, 2H, J¼8.6 Hz), 7.58 (d, 1H, J¼3.8 Hz),
.30 (t, 4H, J¼7.8 Hz), 7.22 (d, 2H, J¼8.5 Hz), 7.18 (d, 4H, J¼7.6 Hz),
.06 (t, 2H, J¼7.3 Hz), 3.60e3.65 (m, 4H), 1.84e1.86 (m, 4H),
3
d
a counter electrode. The active area was controlled at a dimension
2
8
(
7
7
of 0.25 cm by adhering 60
mm thick polyester tape on the Pt
electrode. The photocathode was placed on top of the counter
electrode and was tightly clipped together to form a cell. Electrolyte
was then injected into the seam between two electrodes. Two kinds
of electrolytes were used in order to achieve the best result, i.e.,
system E1 was made of LiI (0.5 M), I (0.05 M), and TBP (4-tert-
2
butylpyridine) (0.5 M) in MeCN, and system E2 was composed of 3-
dimethylimidazolium iodide (DMII)(1.0 M) and guanidinium thio-
13
1
d
.61e1.66 (m, 4H), 1.03e1.10 (m, 6H); C NMR (100 MHz, CDCl
182.7, 155.0, 147.6, 147.5, 142.2, 137.6, 137.1, 134.9, 134.7, 134.2,
30.4, 129.3, 129.1, 128.9, 128.8, 127.9, 126.5, 125.9, 125.1, 124.6,
24.1, 123.7, 123.2, 123.1, 122.7, 121.9, 33.817, 33.640, 27.8, 23.4, 14.1;
3
):
1
1
þ
MS (FAB, 70 eV): m/z (relative intensity) 643 (M , 100); HRMS calcd
for C45 41NOS: 643.2908, found 643.2926.
2
cyanate (0.1 M), in addition to LiI (0.05 M), I (0.03 M), and TBP
H
(0.5 M) in a mixed solvent of MeCN and valeronitrile (85:15, v/v).
Devices made of a commercial dye N719 under the same condition
ꢀ
4
4.1.8. (E)-3-(5-(2-(4-(Diphenylamino)phenyl)-9,10-bis(2-(triiso-pro-
(3ꢁ10 M, Solaronix S.A., Switzerland) was used as a reference.
pylsilyl)ethynyl)anthracen-6-yl)thiophen-2-yl)-2-cyanoacrylic acid
The cell parameters were obtained under an incident light with
ꢀ
2
(AN-TIPS). A mixture of 6a (1.0 g, 1.0 mmol), cyanoacetic acid
intensity 100 mW cm measured by a thermopile probe (Oriel
71964), which was generated by a 300 W Xe lamp (Oriel 6258)
passing through an AM 1.5 filter (Oriel 81088). The current-voltage
parameters of DSSCs were recorded by a potentiostat/galvanostat
model CHI650B (CH Instruments, USA). The light intensity
was further calibrated by an Oriel reference solar cell (Oriel 91150)
and adjusted to be 1.0 sun. The monochromatic quantum efficiency
was recorded through a monochromator (Oriel 74100) at short-
circuit condition. Electrochemical impedance spectra of DSSCs
were recorded by an Impedance/Gain-Phase analyzer (SI 1260,
Solartron).
(
128 mg, 1.50 mmol), and ammonium acetate (20 mg, 0.25 mmol)
in acetic acid was placed in a three-necked flask under a nitrogen
atmosphere and was heated to 90e100 C with stirring for 12 h.
After cooling, the reaction was quenched by adding distilled water,
and extracted with CH
hydrous MgSO and evaporated under vacuum. The product was
purified by silica gel column chromatograph eluted by CH Cl
ꢂ
2 2
Cl . The organic layer was dried over an-
4
2
2
/
acetic acid (19/1). The dark-red solid was isolated in 61% yield
ꢂ
(
584 mg, 0.61 mmol). Mp 176e178 C; IR (KBr)
n
max 3404, 2923,
): 9.02
ꢀ1 1
2
862, 1688, 1566, 1420 cm ; H NMR (400 MHz, DMSO-d
6
d
(
(
d, 1H, J¼1.6 Hz), 8.91 (d, 1H, J¼1.52 Hz), 8.71 (d, 2H, J¼9.0 Hz), 8.39
s, 1H), 8.04e8.11 (m, 2H), 7.94 (d, 1H, J¼4.0 Hz), 7.80 (d, 2H,
4.3. Theoretical calculation
J¼3.6 Hz), 7.77 (s, 1H), 7.27 (t, 4H, J¼7.8 Hz), 7.18 (d, 2H, J¼3.2 Hz),
13
7
.14 (d, 4H, J¼7.8 Hz), 7.04 (t, 2H, J¼7.4 Hz) 1.30e1.35 (m, 42H);
NMR (100 MHz, DMSO-d ): 153.6, 149.3, 148.7, 140.5, 140.1, 134.7,
34.3, 133.4, 133.1, 132.5, 130.3, 129.2, 129.0, 128.8, 128.0, 126.5,
26.3, 125.6, 125.3, 125.2, 124.6, 124.5, 124.2, 120.0, 119.4, 107.1,
C
All organic dyes were optimized by using B3LYP/6-31G* hybrid
functional. Geometry optimizations were performed to locate the
minima on the potential energy surface, in order to predict the
equilibrium structure of a given molecule. For the excited states,
6
d
1
1