ꢀ
62
Z. Bıyıklıoglu / Journal of Organometallic Chemistry 752 (2014) 59e66
Fig. 5. (a) CVs of TiOPc 6. (b) SWV of TiOPc 6.
1599, 1563, 1500, 1396, 1357, 1311, 1283, 1250, 1216, 1200, 1136,
1097, 1024, 988, 968, 833, 755, 687. 1H NMR (CDCl3), (
:ppm): 7.69
68.7, 40.6. UVevis (DMF): lmax, nm (log ): 349 (4.73), 635 (4.42),
3
d
702 (4.95). MALDI-TOF-MS m/z: 1470 [M þ H]þ.
(m, 1H, AreH), 7.26e7.19 (m, 2H, AreH), 7.10 (t, 1H, AreH), 6.59 (d,
1H, AreH), 6.34e6.16 (m, 2H, AreH), 4.24 (m, 2H, eCH2eO), 4.14
(m, 2H, eCH2eO), 3.98e3.91 (m, 4H, eCH2eO), 3.33 (m, 4H, eCH2e
2.1.4. 2(3),9(10),16(17),23(24)-Tetrakis-(2-{2-[3-(diethylamino)
phenoxy]ethoxy}ethoxy)-phthalocyaninato oxotitanium(IV) (6)
Synthesized similarly to 5 from 4. Yield: 0.097 g (38%). IR(KBr
tablet) nmax/cmꢁ1: 3079 (AreH), 2968e2870 (Aliph. CeH), 1609,
1570, 1499, 1450, 1395, 1374, 1278, 1218, 1113, 1074, 1023, 964, 826,
N),1.17 (m, 6H, eCH3). 13C NMR (CDCl3), (
d:ppm): 162.6,160.2,150.1,
135.5, 131.2, 130.1, 121.6, 120.2, 119.7, 117.6, 115.9, 109.6, 106.6, 103.5,
99.1, 70.4, 69.5, 68.9, 67.3, 44.6, 12.9. MS (ESI), (m/z): 380 [M þ H]þ.
749, 686. 1H NMR. (CDCl3), (
d:ppm): 7.76 (m, 4H, AreH), 7.35e7.20
(m, 12H, AreH), 6.43e6.35 (m, 12H, AreH), 4.38 (m, 8H, eCH2eO),
4.18 (m, 8H, eCH2eO), 3.96 (m,16H, eCH2eO), 3.37 (m,16H, eCH2e
2.1.3. 2(3),9(10),16(17),23(24)-Tetrakis-(2-{2-[3-(dimethylamino)
phenoxy]ethoxy}ethoxy)- phthalocyaninato oxotitanium(IV) (5)
N), 1.17 (m, 24H, eCH3). 13C NMR. (CDCl3), (
d:ppm): 160.2, 155.7,
A
mixture of 4-(2-{2-[3-(dimethylamino)phenoxy]ethoxy}
ethoxy)phthalonitrile
3
(0.25 g, 0.71 ꢀ 10ꢁ3 mol), Ti(OBu)4
153.1, 149.3, 149.2, 141.9, 133.5, 129,9, 129,9, 123.8, 110.1, 105.4,
100.8, 99.2, 70.4, 70.2, 67.1, 66.4, 44.4, 12.7. UVevis (DMF): lmax, nm
(0.25 ꢀ 10ꢁ3 L, 0.71 ꢀ 10ꢁ3 mol), 5 drops of 1.8-diazabicyclo[5.4.0]
undec-7-ene (DBU) in n-pentanol (0.0025 L) was refluxed with
stirring for 12 h under N2. After cooling to room temperature, 0.03 L
ethanol was added to precipitate the product. The precipitate was
filtered and dried in vacuo. Lastly, purification was achieved using
column chromatography with basic alumina as column material
(log
3
): 347 (4.62), 634 (4.31), 704 (4.85). MALDI-TOF-MS m/z: 1582
[M]þ.
2.1.5. 2(3),9(10),16(17),23(24)-Tetrakis-(2-{2-[3-(dimethylamino)
phenoxy]ethoxy}ethoxy)- phthalocyaninato oxotitanium(IV)iodide
(5a)
and CHCl3 as eluent. Yield: 0.158 g (61%). IR(KBr tablet) nmax/cmꢁ1
:
3077 (AreH), 2924e2869 (Aliph. CeH), 1604, 1573, 1486, 1447,
Titanium(IV) phthalocyanine 5 (0.045 g, 0.03 ꢀ 10ꢁ3 mol) was
resolved in 0.003 L of CHCl3 and 0.004 L iodomethane was added to
this solution. This reaction mixture was stirred at room tempera-
ture for 5 days. The precipitate was filtered off, washed with
chloroform, acetone and diethyl ether. Then, water-soluble ionic
titanium(IV) phthalocyanine was dried in vacuo. Yield: 0.043 g
1394, 1338, 1283, 1232, 1118, 1058, 998, 958, 822, 747, 685. 1H NMR.
(CDCl3), (
6.44e6.32 (m, 12H, AreH), 4.37e4.17 (m, 32H, eCH2eO), 2.95 (s,
24H, eCH3). 13C NMR. (CDCl3), (
:ppm): 159.0, 152.7, 150.2, 139.8,
135.3, 131.5, 127.9, 125.3, 121.4, 112.6, 108.5, 107.9, 106.5, 100.6, 69.7,
d:ppm): 7.78 (m, 4H, AreH), 7.24e7.18 (m, 12H, AreH),
d