M.O. Liu et al. / Journal of Organometallic Chemistry 689 (2004) 1078–1084
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18.1 mmol) and N; N-dimethylformamide (DMF)
(15 ml) were irradiated in a quartz vessel of 50 ml by a
microwave oven at 440 W for 10 min. After washed with
a methanol/water solution (v/v ¼ 1/1) and purified by
recystallization with methanol, 4-cumylphenoxy-4-pht-
halonitrile (3.06 g) was obtained (yield: 78%). IR (KBr)
(cmꢀ1) (4-cumylphenoxy-4-phthalonitrile): 3050, 2914,
2250, 1601, 1511, 1300, 1242, 1184, 1096, 1010, 910, 821,
786, 711, 592, 575.
4-Cumylphenoxy-4-phthalonitrile (1 g, 2.96 mmol)
and copper chloride (0.2 g, 1.49 mmol) in the presence of
1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) (5 ml) were
irradiated in a quartz vessel of 50 ml by a microwave
oven at 440 W for 10 min. The product was washed with
a methanol/water solution (v/v, 1/2) and purified by
column chromatography (silica gel, tetrahydrofuran/
ethyl acetate/methanol ¼ 4/1/1, wt/wt/wt). After drying,
CuPc(b-CP)4 (0.81 g) was obtained (yield: 77%). IR
(KBr) (cmꢀ1) (CuPc(b-CP)4): 3047, 2952, 1615, 1604,
1512, 1445, 1344, 1317, 1251, 1221, 1190, 1132, 1085,
radiated in a quartz vessel of 50 ml by a microwave oven
at 560 W for 5 min. The crude product was washed with
distilled water and purified by recystallization with tol-
uene. After purified by column chromatography (alu-
minum oxide, chloroform), H2(TBP) (2.18 g) was
obtained (yield: 56%).
IR (KBr) (cmꢀ1) (H2(TBP)): 3416, 2959, 2853, 1664,
1646, 1601, 1568, 1550, 1531, 1502, 1465, 1410, 1391,
1362, 1329, 1295, 1266, 1196, 1155, 1141, 1107, 1089,
1019, 960, 879, 838, 764, 709, 665, 558, 425. UV–Vis
kmax (nm) 545, 513, 415 (in ethanol). MS: (m=z) (FABþ)
840. Elemental analysis for C60H62N4, Calc. C, 85.88; H,
7.45 ; N, 6.68. Found: C, 85.72; H, 7.33; N, 6.52%.
H2(TBP) (1 g, 1.2 mmol) and magnesium chloride
(0.17 g, 1.79 mmol) were ground together in a quartz
vessel of 50 ml, poured into 1,8-diazabicyclo [5.4.0]
undec-7-ene (DBU, 5 ml) as catalyst, and irradiated in a
microwave oven at 240 W for 5 min. The crude product
was firstly dissolved in ethanol, and then butyl acetate as
well as petroleum ether was added for precipitation.
After purified by recystallization with methanol and by
column chromatography (aluminum oxide, chloroform),
Mg(TBP)(0.75 g) was obtained (yield ¼ 72%).
1043, 912, 817, 740, 661, 622 cmꢀ1. UV [toluene, kmax
]
680, 612, 349 nm. MS: m=z 1417 (FABþ). Elemental
analysis for C92H72N8O4Cu, Calc. C, 77.97; H, 5.12 ; N,
7.91. Found: C, 77.83; H, 5.19; N, 7.57%.
IR (KBr) (cmꢀ1) (Mg(TBP)): 2941, 2857, 1664, 1644,
1611, 1552, 1535, 1513, 1482, 1465, 1443, 1387, 1359,
1320, 1267, 1233, 1200, 1107, 1020, 990, 956, 914, 883,
836, 794, 716, 665, 647, 536, 514, 464, 441. UV–Vis kmax
(nm) 610, 565, 431 (in 1-methyl-2-pyrrolidone (NMP)).
MS: (m=z) (FABþ) 861. Elemental analysis for
C60H60N4Mg, Calc. C, 83.65; H, 7.02 ; N, 6.50. Found:
C, 85.55; H, 7.13; N, 6.35%.
The same procedure was adopted in the preparation
of CuPc(a-CP)4 except that the starting material was 3-
nitrophthalonitrile. The yield was 71%. IR (KBr) (cmꢀ1
)
(CuPc(a-CP)4): 3045, 2951, 1613, 1602, 1515, 1441,
1341, 1315, 1253, 1219, 1192, 1131, 1081, 1042, 915,
813, 742, 657, 618 cmꢀ1. UV [toluene, kmax] 695, 625,
334 nm. MS: m=z 1417 (FABþ). Elemental analysis for
C92H72N8O4Cu, Calc. C, 77.97; H, 5.12 ; N, 7.91.
Found: C, 77.69; H, 5.20; N, 7.20%.
The same procedure was adopted in the preparation
of Zn(TBP), Cu(TBP), InCl(TBP), and AlCl(TBP). The
yields of Zn(TBP), Cu(TBP), InCl(TBP), and
AlCl(TBP) were 65%, 77%, 71%, 68%, respectively.
IR (KBr) (cmꢀ1) (Zn(TBP)): 2952, 1719, 1636, 1561,
1462, 1269, 1191, 1096, 1011, 972, 845, 799, 741, 559. UV–
Vis kmax (nm) 612, 551, 425 (in NMP). MS: (m=z) (FABþ)
902. Elemental analysis for C60H60N4Zn, Calc. C, 79.85;
H, 6.70; N, 6.21. Found: C, 79.72; H, 6.81; N, 6.13%.
IR (KBr) (cmꢀ1) (Cu(TBP)): 2947, 1715, 1632, 1558,
1467, 1267, 1188, 1092, 1016, 975, 848, 802, 745, 554. UV–
Vis kmax (nm) 609, 543, 419 (in NMP). MS: (m=z) (FABþ)
900. Elemental analysis for C60H60N4Cu, Calc. C, 80.01;
H, 6.71; N, 6.22. Found: C, 79.88; H, 6.65; N, 6.11%.
IR (KBr) (cmꢀ1) (InCl(TBP)): 2950, 1716, 1631, 1557,
1458, 1261, 1184, 1096, 1018, 971, 850, 805, 747, 551. UV–
Vis kmax (nm) 615, 561, 428 (in NMP). MS: (m=z) (FABþ)
951. Elemental analysis for C60H60N4InCl, Calc. C, 72.98;
H, 6.12; N, 5.67. Found: C, 72.85; H, 6.03; N, 5.72%.
IR (KBr) (cmꢀ1) (AlCl(TBP)): 2955, 1711, 1628,
1563, 1455, 1253, 1177, 1092, 1011, 965, 853, 801,
752, 555. UV–Vis kmax (nm) 618, 564, 430 (in NMP).
MS: (m=z) (FABþ) 899. Elemental analysis for
C60H60N4AlCl, Calc. C, 80.11; H, 6.72; N, 6.23. Found:
C, 80.22; H, 6.66; N, 6.26%.
2.1.2. Preparation of tetrakis(2,9,16,23-tert-butyl) cop-
per phthalocyanines (CuPc(b-t-butyl)4) (Scheme 3)
4-tetra-t-Butyl phthalonitrile (1 g, 5.44 mmol) and
copper chloride (0.37 g, 2.72 mmol) in the presence of 1,8-
diazabicyclo [5.4.0] undec-7-ene (DBU) (5 ml) were irra-
diated in a quartz vessel of 50 ml by a microwave oven at
440 W for 10 min. The product was washed with a
methanol/water solution (v/v, 1/2) and purified by column
chromatography (silica gel, ethyl acetate/n-hexane ¼ 1/4,
wt/wt). After drying, CuPc(b-t-butyl)4 (0.81 g) was ob-
tained (yield: 74%). IR (KBr)(CuPc(b-t-butyl)4): 2953,
1611, 1609, 1448, 1359, 1317, 1253, 1221, 1195, 1140,
1088, 1046, 914, 822, 742, 665, 532, 503 cmꢀ1. UV [tolu-
ene, kmax] 677, 610, 346 nm. MS: m=z 800 (FABþ). Ele-
mental analysis for C48H48N8Cu:, Calc. C, 72.02; H, 6.04 ;
N, 14.00. Found: C, 72.31; H, 6.27; N, 13.80%.
2.1.3. Preparation of 5,10,15,20-tetrakis(4-tert-butylphe-
nyl)porphyrins ((M(TBP), M ¼ H2, Mg, Zn, Cu, InCl,
AlCl) (Scheme 4)
4-tertbutyl benzaldehyde (3 g, 18.5 mmol), pyrrole
(1.34 g, 20 mmol), and propionic acid (10 ml) were ir-