B2+B3
a/b
13
temperature overnight, during which time a yellow precipitate
formed. The solid was collected by filtration, washed with EtOH
and dried in vacuo. The crude solid was recrystallized from hot
7.54 (m, 8H, H
), 7.54 (d, J = 16.0 Hz, 2H, H ). C NMR
C O A2
(126 MHz, CD CN) d (ppm) 188.6 (C ), 152.5 (C ), 144.0
3
a/b
B1/B4 B10 B2/B3 a/b
(C ), 130.1 (C
), 130.0 (C ), 128.5 (C
), 128.2 (C ), 126.6
), 123.4 (C ), quaternary C not resolved. IR
◦
B1/B4
B2/B3
A3
EtOH to give orange crystals (1.05 g, 70.0%). m.p. 168–170 C.
(C
), 126.1 (C
1
-1
H NMR (500 MHz, CDCl
3
) d (ppm) 8.86 (overlapping d (J =
(solid, cm ): 3054 w, 1669 s, 1653 m, 1590 s, 1558 s, 1424 m, 1357
w, 1295 w, 1265 s, 1230 w, 1209 m, 1063 w, 1038 w, 1015 m, 984 m,
a/b+A2
B10
1
8
(
7
(
(
(
5.9 Hz) and d(AB) (J = 6.0 Hz), 3H, H
), 8.50 (s, 1H, H ),
B1
B4
.27 (d, J = 8.5 Hz, 2H, H ), 8.04 (d, J = 8.3 Hz, 2H, H ), 7.82
965 m, 852 s, 814 s, 744 m, 733 s. ESI MS (CH
2
Cl /MeOH) m/z
2
A3
B2+B3
+
+
d
(AB), J = 6.1 Hz, 2H, H ), 7.57–7.51 (overlapping, 4H, H
),
) d
), 130.1
727.2 [M - SbF
6
] (calc. 727.1), 416.0 [M - SbF
6
- 2] (calc. 416.0),
a/b
13
+
.49 (d, J = 15.9 Hz, 1H, H ). C NMR (126 MHz, CDCl
ppm) 189.2 (C ), 151.2 (C ), 144.1 (C ), 131.5 (C
3
310.1 [2 + H] (base peak, calc. 310.1). Found C 54.74, H 3.20, N
C
O
A2
a/b
B4a/B9a
3.03; C44
H
30AgF
6
N
2
O
2
Sb requires C 54.92, H 3.14, N 2.91%.
a/b
B4a/B9a
B9
B10
B4
C
C
), 129.9 (C
), 129.5 (C ), 129.3 (C ), 129.25 (C ), 127.0
), 125.2 (C ), 121.8 (C ), C not observed.
B2/B3
B2/B3
B1
A3
A4
), 125.7 (C
[
Ag{(Z)-2}
2
][SbF
6
]
-
1
IR (solid, cm ): 3046 w, 1662 s, 1597 s, 1587 s, 1576 m, 1441 w,
3
1
9
1
3
7
411 m, 1355 m, 1334 w, 1291 m, 1266 m, 1208 m, 1063 w, 1024 m,
(Z)-2 (30.9 mg, 0.10 mmol) was dissolved in CH
a solution of AgSbF (17.1 mg, 0.050 mmol) in MeOH (4 cm )
was added. The reaction mixture was stirred at room temperature
for 10 min and then filtered. The filtrate was allowed to evaporate
at room temperature, and an orange precipitate formed in 3 days.
This was collected by decanting the solvent, was washed with
2
Cl
2
(8 cm ) and
3
73 s, 930 w, 892 m, 804 s, 784 m, 731 s. UV/VIS lmax/nm (5.0 ¥
6
-
6
-3
3
3
-1
-1
0 mol dm , CH
2
Cl
2
), 256 (e/10 dm mol cm 133), 351 (4.58),
Cl /MeOH) m/z
05.6 [2M + Na + 2MeOH] , 641.2 [2M + Na] (calc. 641.2), 332.2
68 (5.80), 388 (5.88), 430sh (3.20). ESI MS (CH
2
2
+
+
+
+
[M + Na] (base peak, calc. 332.1), 310.3 [M + H] (calc. 310.1).
Found C 84.34, H 5.16, N 4.61; C22
4.22, H 5.18, N 4.37%.
H
15NO·0.25EtOH requires C
MeOH and dried in air. [Ag{(Z)-2}
2
][SbF
6
] was isolated as an
CN) d
1
8
orange solid (36.0 mg, 75.0%). H NMR (500 MHz, CD
3
A2
B10
(
(
(
ppm) 8.41 (s, 2H, H ), 8.32 (d(AB), J = 6.1 Hz, 4H, H ), 8.07
a/b B1/B4 B1/B4
overlapping m, 6H, H + H
overlapping m, 10H, H + H
), 8.00 (m, 4H, H
), 7.34 (d(AB), J = 6.1 Hz, 4H,
), 7.48
Compound (Z)-2
E)-2 (8.0 mg, 0.026 mmol) was dissolved in CDCl
a/b
B2+B3
3
A3
13
C
O
(
3
(0.6 cm ) in
H ). C NMR (126 MHz, CDCl ) d (ppm) 193.0 (C ), 151.2
B9/B9a/B4a a/b
3
A2
A4
a/b
an NMR tube. The tube was exposed to sunlight for 3 days, after
(C ), 144.9 (C ), 142.4 (C ), 132.1 (C
), 131.2 (C ),
B9/B9a/B4a
B1/B4
B10
B2/B3
which time the solvent was removed. The residue was redissolved in
129.75 (C
(C
), 129.7 (C
), 128.2 (C ), 127.2 (C
), 126.5
3
B1/B4
B2/B3
A3
CH
2
Cl
2
/MeOH (1.0 cm , 3 : 1 v/v) in a small vial, and the solvent
), 126.3 (C
), 122.0 (C ), one quaternary C not observed.
IR (solid, cm ): 1665 m, 1595 m, 1443 w, 1418 m, 1232 m, 1217
m, 1001 m, 893 m, 841 w, 785 m, 778 m, 745 s, 735 s, 724 s, 653
-
1
was allowed to evaporate slowly. Over a period of 3 days, X-ray
quality yellow needles formed which were collected by filtration,
washed with MeOH and dried in vacuo. (Z)-2 was isolated as
-
6
-3
3
s. UV/VIS lmax/nm (2.9 ¥ 10 mol dm , acetone), 348 sh (e/10
◦
1
dm mol cm-1 8.38), 368 (11.3), 385 (12.0), 416 sh (6.31). ESI
3
-1
yellow needles (6.5 mg, 81%). m.p. 160–162 C. H NMR (500
B10
+
MHz, CDCl
3
) d (ppm) 8.26 (s, 1H, H ), 8.12 (d, J = 5.6 Hz, 2H,
MS (MeOH) m/z 641.3 [Na(2)
[Na(2)] (calc. 332.1). FAB MS (NBA matrix) m/z 727.1 [M -
2
] (base peak, calc. 641.2), 332.1
A2
a/b
B1/B4
+
H ), 8.08 (d, J = 12.1 Hz, 1H, H ), 8.02 (d, J = 8.7 Hz, 2H, H
),
), 7.43 (m, 2H,
), 7.21 (d, J = 12.1 Hz, 1H, H ) 7.02 (d, J = 5.6 Hz, 2H,
B1/B4
B2/B3
+
+
7
H
.89 (d, J = 8.4 Hz, 2H, H
), 7.48 (m, 2H, H
SbF
6
] (calc. 727.1) 416.0 [M - SbF
6
- 2] (base peak, calc. 416.0).
B2/B3
a/b
Found C 54.11, H 3.29, N 2.86; C44
C 53.91, H 3.45, N 2.82%.
H
30AgF
6
N
2
O
2
Sb·H
2
O requires
A3
13
C O
H ). C NMR (126 MHz, CDCl
3
) d (ppm) 193.4 (C ), 149.5
A2
a/b
B4a/B9a
a/b
B4a/B9a
(
1
1
C ), 141.3 (C ), 130.9 (C
), 130.7 (C ), 129.3 (C
),
B9
B1/B4
B10
B2/B3
B1/B4
29.5 (C ), 129.0 (C
),128.1 (C ), 126.5 (C
), 125.3 (C
),
Compound (E)-3
B2/B3
A3
A4
-6
25.1 (C
), 120.5 (C ), C not observed. UV/VIS (5.8 ¥ 10
3 3
-
3
-1
-1
mol dm , CH
2
Cl
2
) lmax/nm 257 (e/10 dm mol cm 124), 349sh
Cl /MeOH)
m/z 332.1 [M + Na ] (base peak, calc. 332.1), 310.2 [M + H] (calc.
9-Acetylanthracene (1.10 g, 5.00 mmol) and pyridine-4-
carbaldehyde (0.535 g, 5.00 mmol) were suspended in EtOH
(
4.83), 368 (6.21), 388 (6.21), 417 (3.90). ESI MS (CH
2
2
+
+
3
(15 cm ). The mixture was stirred as aqueous KOH (0.336 g, 6.00
3
3
10.1). Found C 84.71, H 5.06, N 4.51; C22
H
15NO requires C 85.41,
mmol in 4.0 cm H
2
O) was added, and was then stirred at room
H 4.89, N 4.53.
temperature overnight. A yellow solid formed which was collected
by filtration, washed with EtOH and dried in vacuo. (E)-3 was
◦
1
isolated as a yellow solid (0.800 g, 51.8%). m.p. 179–180 C. H
[
Ag{(E)-2}
2
][SbF ]
6
A2
NMR (500 MHz, CDCl ) d (ppm) 8.58 (d, J = 5.9 Hz, 2H, H ),
B4 B1
3
3
B10
AgSbF
6
(17.1 mg, 0.050 mmol) was dissolved in MeOH (4 cm )
8.56 (s, 1H, H ), 8.06 (m, 2H, H ), 7.85 (m, 2H, H ), 7.48 (m,
3
B2+B3
a/b
and a solution of (E)-2 (30.9 mg, 0.10 mmol) in CH
2
Cl
2
(8 cm )
4H, H
), 7.37 (d, J = 16.3 Hz, 1H, H ), 7.25 (d, J = 5.7 Hz, 2H,
H ), 7.14 (d, J = 16.3 Hz, 1H, H ). C NMR (126 MHz, CDCl )
d (ppm) 199.9 (C ), 150.8 (C ), 144.3 (C ), 141.7 (C ), 133.9
), 129.0 (C ),
), 125.1 (C ), 122.2 (C ).
IR (solid, cm ): 3054 w, 1642 s, 1624 m, 1593 m, 1548 w, 1447 w,
1414 m, 1356 m, 1289 w, 1265 m, 1231 m, 1215 s, 1185 s, 1168 w,
1152 m, 1143 w, 1091 w, 1013 w, 982 s, 948 w, 885 s, 845 s, 811 s, 728
A3
a/b
13
was added. The reaction mixture was stirred at room temperature
for 10 min and was then filtered. The filtrate was left to evaporate
slowly at room temperature. Red crystals of X-ray quality formed
over a period of 3–7 days, were collected by decanting the solvent
3
C
O
A2
a/b
A4
B9
a/b
B4a/B9a
B4a/B9a
B4
(C ), 132.8 (C ), 131.3 (C
), 129.2 (C
B10
B2/B3
B2/B3
B1
A3
128.6 (C ), 127.2 (C
), 125.8 (C
-
1
and were washed with MeOH three times and dried in air. [Ag{(E)-
1
2
(
8
H
}
2
][SbF
400 MHz, CD
6
] was isolated as red crystals (33.2 mg, 69.2%). H NMR
A2
3
CN) d (ppm) 8.81 (d(AB), J = 6.1 Hz, 4H, H ),
a/b
B10
-6
-3
.74 (d, J = 16.0 Hz, 2H, H ), 8.62 (s, 2H, H ), 8.32 (m, 4H,
s, 694 s, 670 s. UV/VIS lmax/nm (5.0 ¥ 10 mol dm , CH
2
Cl ), 256
2
B1/B4
B1/B4
A3
3
3
-1
-1
), 8.12 (m, 4H, H
), 7.93 (d(AB), J = 6.1 Hz, 4H, H ), 7.61–
(e/10 dm mol cm 150), 276 sh (24.2), 347 (5.88), 365 (7.20),
This journal is © The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 12146–12152 | 12147