SAKA ET AL.
3 of 9
7
.37 (m, 4H, Ar―H), 7.30–7.15 (m, 4H, Ar―H), 7.10 (s,
ethanol (30 ml), filtered off again and washed with hot
ethanol, distilled water and diethyl ether. After drying
under vacuum, the product was purified on basic alumina
column with chloroform–methanol (92:8) for compound
6, (95:5) for compound 7 solvent system as eluent.
H, Ar―H). 13C NMR (CDCl3), (d: ppm): 162.10 (CH¼N),
1
1
1
1
2
61.09 (ArC―O), 148.05 (ArC―N), 134.51, 133.66,
32.25, 131.98, 130.68, 129.68, 128.60, 128.53, 127.66,
26.55, 125.80, 124.77, 123.61, 122.44, 120.18, 118.55,
17.33, 116.47. MS (ESI), (m/z): C H NO Calculated:
21
15
+
96.35; Found: 297.48 [M + H] .
2.5.4 | Synthesis of Cobalt (II) phthalocya-
nine (6)
2
.5.2 | Synthesis of (E)‐4‐(4‐((anthracen‐9‐
Yield: 200 mg (38%). Mp >300 °C. Anal.calc. For
ylmethylene)amino)phenoxy)
phthalonitrile (5)
−
1
C117H O N Co FT‐IR νmax/cm
(KBr pellet): 3088,
72
4 12
3045 (Ar‐H), 2992, 2866 (Aliph. C‐H), 1732, 1644, 1506,
4‐Nitrophthalonitrile 4 (1.10 g, 6.41 mmol) was dissolved
1488, 1451, 1388, 1326, 1287, 1266, 1179, 1098, 1022,
in 10 ml dry DMF under N atmosphere, and of (E)‐4‐
986, 956, 872, 765, 721, 703, 699. UV–Vis (CHCI ): λmax,
2
3
(
6
(anthracen‐9‐ylmethylene)amino) phenol 3 (1.19 g,
.41 mmol) added to mixture. After stirring for 30 min
at 60 °C, finely ground anhydrous K CO3 (2.65 g,
nm (log ε): 676 (4.72), 610 (4.45), 330 (4.88). MALDI‐
TOF‐MS, (m/z): Calculated: 1768.83; Found:1769.38
+
[M + H] C117H O N Co: calcd. C 79.45; H 4.10; N
2
72 4 12
1
9.23 mmol) was added portion wise within 2 h. The reac-
9.50%; found: C 79.50; H 4.15; N 9.55.
tion mixture was stirred under N at 60 °C for 3 days. At
2
the end of this time, the reaction mixture was poured into
ice‐water and stirred at room temperature for 3 h to yield
a crude product. The mixture was filtered and dried in
vacuum over P O for 4 h and recystallized from ethanol
2
.5.5 | Synthesis of Copper (II) phthalocy-
anine (7)
Yield: 220 mg (42%). Mp >300 °C. Anal.calc. For
C117H O N Cu FT‐IR νmax/cm
2
5
−
1
to give bright brown crystalline powder. Yield: 1.95 g
(KBr pellet): 3092,
72
4 12
(
(
(
1
9
7
7
72%). mp: 144‐145 °C. Anal.calc. For C H N O IR
KBr pellet), νmax/cm : 3085, 3040 (Ar‐H), 2926, 2860
Aliph. C‐H), 2231 (C°N), 1672 (C‐O), 1627, 1561, 1588,
3045, 3002 (Ar‐H), 2986, 2923, 2860 (Aliph. C‐H), 1740,
1605, 1522, 1455, 1440, 1386, 1365, 1288, 1233, 1162,
1089, 1026, 988, 923, 879, 853, 772, 744. UV–Vis (CHCI3):
λmax, nm (log ε): 672 (4.98), 617 (4.44), 327 (4.62).
MALDI‐TOF‐MS, +(m/z): Calculated:1773.44; Found:
1174.20 [M + H] C117H O N12Cu: calcd. Calcd. C
29
17 3
−
1
484, 1444, 1285, 1251, 1196, 1161, 1099, 1087, 969, 953,
1
26, 796, 777, 731, 655. H‐NMR. (CDCl ), (δ:ppm):
3
.96–7.88 (m, 4H, Ar‐H), 7.80–7.68 (m, 4H, Ar‐H), 7,62–
.48 (m, 4H, Ar‐H), 7.38–7.25 (m, 3H, Ar‐H) 7.14 (s, H,
72
4
79.24; H 4.09; N 9.48%; found: C 77.36; H 4.12; N 10.00.
13
Ar‐H), 7.10 (s, H, CH¼N). C‐NMR. (CDCl ), (δ:ppm):
3
1
61.90 (C15 ¼ N), 154.39 (C ‐O), 150.86 (C ‐O), 141.40
22
19
3
| RESULTS AND DISCUSSION
.1 | Synthesis and characterization
(
(
(
C ), 140.59 (C ), 136.44 (C ), 135.56 (C ), 134.49
C ), 133.72 (C ) 132.80 (C ), 131.28 (C ), 130.67
C ), 129.66 (C ), 128.80 (C ), 127.46 (C ), 126.57 (C ‐
16 1 23 27
24
25
26
20
3
21
17
8
18
5
C ), 125.33 (C ‐C ), 124.68 (C ‐C ), 122.38 (C ‐C ),
All synthetic pathways for new cobalt (II) and copper
(II) phthalocyanine compounds were outlined in
Figure 1. The condensation of 9‐anthraldehyde 1 with
4‐aminophenol 2 in dry ethanol at 1:1 ratio gave the
expected (E)‐4‐((anthracen‐9‐ylmethylene)amino) phenol
4
3
6
7
2
9
14
1
1
4
21.80 (C ‐C ), 120.43 (C ‐C ), 117.51 (C ≡ N),
10
13
11 12
28
15.61 (C29 ≡ N). MALDI‐TOF‐MS, (m/z): Calculated:
+
23.46; Found: 441.36 [M + H O] C H N O.
2
29 17 3
[
29]
3
(Schiff base) in a high yield (76.65%).
In the IR
2.5.3 | General Procedure of Metal Phtha-
spectrum of 3, the disappearing of the intense absorption
locyanines 6–7
−
1
bands at 3388 and 3360 cm , corresponding to the –NH
2
To give the metal phthalocyanies, the mixture of
phthalonitrile compound 5 (0.5 g, 1.18 mmol), the related
groups of 2, after the conversion to substituted Schiff base
−
1
and the appearance of a new band at 1612 cm corre-
sponding to CH¼N group, indicated that the combining
has occurred. Moreover, in the same spectrum of 3, the
anhydrous metal salt (CoCl ) (38.19 mg, 0.295 mmol) for
2
compound 6, CuCl (39.69 mg, 0.295 mmol) for com-
2
−
1
pound 7 and two drops of DBU was heated at 160 °C in
dry n‐pentanol (3 mL) in a sealead tube, and stirred for
disapearing of sharp absorbtion band at 1700 cm
(C¼O) of 1and the appearance of new band at 1612 cm
−
1
2
4 h. At the end of the reaction, green product was pre-
indicated that the combining has successfully occured.
The rest of the spectrum of the Schiff base 3 resembles
closely that of starting reactants 1 and 2 including the
cipitated by addition of ethanol (20 ml) and filtered off.
Along 2 hours, the green solid product was refluxed with