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L. Zhang et al. / Bioorg. Med. Chem. 16 (2008) 303–312
d = 151.58, 133.45, 138.77, 135.04, 128.44, 122.76, 120.32,
63.46, 58.85, 45.81, 31.31. UV/Vis (H2O): kmax
(loge) = 353 (3.78), nm 656 (3.9). elemental analysis calcd
(%) for C60H80N12S4I4ZnÆ6H2O: C, 40.05; H, 5.18; N,
9.46; Found: C, 40.01; H, 4.91; N, 9.38. TG weight loss
was found at 210 ꢁC, 6H2O.
Vis (H2O): kmax (loge) = 328 (3.8), 632 nm (3.7). Ele-
mental analysis calcd (%) for C52H66N12O4I4Æ2H2O: C,
42.60; H, 4.64; N, 11.46. Found: C, 42.53; H, 4.81; N,
11.61. TG weight loss was found at 160 ꢁC, 2H2O.
4.6.6. Tetrakis(2-trimethylaminoethylethanol)phthalo cyan-
inato zinc tetraiodine (6).12 Compound 22 (30 mg,
0.032 mmol) was dissolved in CHCl3 (5 mL), and methyl
iodide (0.15 g, 1.059 mmol) was added to this solution.
The mixture was refluxed for 4 h. Then the reaction was
treated according to 5.1.5. Yield: 45 mg (93%) 1H NMR
(300 MHz, DMSO-d6) d 9.33 (br, 4H), 8.97 (br, 4H),
7.88 (br, 4 H), 5.09 (br, 8H), 4.09 (br, 8H), 3.38 (br,
36H). 13C NMR d = 160.16, 152.68, 140.57, 132.27,
124.39, 119.18, 107.11, 65.21, 63.67, 54.19. UV/Vis
(H2O): kmax (loge) = 337 (3.9), 633 nm (3.9).
4.6.2. Tetrakis(2-trimethylaminolethylsulfanyl)phthalo cyan-
inato zinc tetraiodine (2). Compound 18 (25 mg,
0.027 mmol) was dissolved in CHCl3 (5 mL), and methyl
iodide (0.15 g, 1.059 mmol) was added to this solution.
The mixture was refluxed for 4 h. Then the reaction was
treated according to 5.1.5. Yield: 28 mg (88%). (Found:
1
C, H NMR (300 MHz, DMSO-d6) d = 9.39 (br, 8H),
8.29 (br, 4H), 3.91 (br, 8H), 3.80 (br, 8H), 3.29 (br,
36H). 13C NMR d = 153.09, 139.52, 137.04, 136.51,
130.42, 123.77, 121.51. UV/Vis (H2O): kmax (loge) = 344
(3.8), 642 nm (3.8). Elemental analysis calcd (%) for
C52H64N12S4I4ZnÆ6H2O: C, 37.67; H; 4.69; N, 9.88.
Found: C, 37.50; H, 4.57; N, 10.1. TG weight loss was
found at 210 ꢁC, 6H2O.
4.6.7. Tetrakis(2-trimethylaminoethylethanol)phthalo cyan-
inato nickel tetraiodine (7). Compound 23 (20 mg,
0.0216 mmol) was dissolved in CHCl3 (5 mL), and methyl
iodide (0.15 g, 1.059 mmol) was added to this solution.
The mixture was refluxed for 4 h. Then the reaction was
treated according to 5.1.5. Yield: 30 mg (94%). 1H
NMR (300 MHz, DMSO-d6) 1H NMR (300 MHz,
DMSO-d6) d = 9.89 (br, 8H), 7.77 (br, 4H), 5.04 (br,
8H), 4.24 (br, 8 H), 3.48 (br, 36H). 13C NMR
d = 160.13, 148.28, 137.56, 129.46, 124.21, 119.57,
106.79, 65.15, 63.76, 54.35. UV/Vis (H2O): kmax
(loge) = 276 (3.8), 622 nm (3.7). Elemental analysis calcd
(%) for C52H64N12O4I4NiÆ5H2O: C, 39.55; H, 4.69; N,
10.65. Found: C, 39.60; H, 4.57; N, 10.70. TG 6.2; TG
weight loss was found at 200 ꢁC, 5H2O.
4.6.3. 4-[1,3-Bis-(trimethylamino)2-propyloxy]phthalo-cyan-
inato zinc octaiodine (3). Compound 19 (25 mg,
0.021 mmol) was dissolved in CHCl3 (10 mL), and methyl
iodide (0.15 g, 1.059 mmol) was added to this solution.
The mixture was refluxed for 4 h. Then the reaction was
treated according to 5.1.5. Yield: 47 mg (96%). 1H
NMR (300 MHz, DMSO-d6) d 9.37 (br, 8H), 8.20 (br,
4H), 6.30 (br, 4 H), 4.19 (br, 16H), 3.43 (br, 72H). 13C
NMR d = 161.69, 150.99, 144.09, 137.33, 129.83,
126.84, 115.44, 74.51, 72.18, 59.514. UV/Vis (H2O): kmax
(loge) = 168 (3.9), 667 nm (4.2). elemental analysis calcd
(%) for C60H104N16O4I8NiÆ4H2O: C, 34.66; H, 4.79; N,
9.53. Found: C, 34.74; H, 4.79; N, 9.55. TG weight loss
was found at 155 ꢁC, 4H2O.
4.6.8. Tetrakis(2-trimethylaminolethylsulfanyl)phthalo cyan-
inato tetraiodine (8). Compound 24 (30 mg, 0.027 mmol)
was dissolved in CHCl3 (5 mL), and methyl iodide
(0.15 g, 1.059 mmol) was added to this solution. The
mixture was refluxed for 4 h. Then the reaction was
treated according to 5.1.5. Yield: 31 mg (95%). 1H
NMR (300 MHz, DMSO-d6) d = 9.36 (br, 4H), 8.98 (br,
4H), 7.97 (br, 4 H), 5.11 (br, 8H), 4.15 (br, 8H), 3.42
(br, 36H). 13C NMR d = 152.56, 143.22, 140.51, 137.76,
135.12, 128.25, 126.86, 69.34, 58.19, 31.72. UV/Vis
(H2O): kmax (loge) = 331 (3.7), 637 nm (3.7). Elemental
analysis calcd (%) for C52H66N12S4I4Æ2H2O: C, 40.75;
H, 4.57; N, 10.98. Found: C, 40.59; H, 4.71; N,
10.77. TG 6.2; TG weight loss was found at 190 ꢁC,
2H2O.
4.6.4. Tetrakis(N,N,N-diethyl-methyl-2-aminolethyl sul-
fanyl)phthalocyaninato tetraiodine (4). Compound 20
(18 mg, 0.021 mmol) was dissolved in CHCl3 (5 mL),
and methyl iodide (0.15 g, 1.059 mmol) was added to
this solution. The mixture was refluxed for 4 h. Then
the reaction was treated according to 5.1.5. Yield:
1
28 mg (93%). H NMR (300 MHz, DMSO-d6) d = 9.34
(br, 8H), 8.40 (br, 4H), 3.98 (br, 8 H), 3.75 (br, 8H),
3.57 (br, 12H), 3.18 (br, 16H), 1.34 (br, 24H). 13C
NMR d = 148.09, 138.47, 135.82, 133.18, 130.78,
123.47, 121.54, 59.17, 56.67, 47.67, 26.58, 8.61. UV/Vis
(H2O): kmax (loge) = 331 (3.8), 638 nm (3.8). Elemental
analysis calcd (%) for C60H82N12S4I4Æ5H2O: C, 42.41;
H, 5.42; N, 9.88. Found: C, 42.14; H, 5.11; N, 9.78.
TG weight loss was found at 190 ꢁC, 5H2O.
4.6.9. Octakis(2-trimethylaminoethylsulfanyl)phtha-loc-
yaninato zinc octaiodine (9).14 Compound 25 (33 mg,
0.025 mmol) was dissolved in CHCl3 (5 mL), and methyl
iodide (0.15 g, 1.059 mmol) was added to this solution.
The mixture was refluxed for 4 h. Then the reaction
4.6.5.
Tetrakis(2-trimethylaminoethylethanol)phthalo-
1
cyaninato tetraiodine (5). Compound 21 (15 mg,
0.016 mmol) was dissolved in CHCl3 (5 mL), and methyl
iodide (0.15 g, 1.059 mmol) was added to this solution.
The mixture was refluxed for 4 h. Then the reaction
was treated according to 5.1.5. Yield: 56 mg (91%). H
NMR (300 MHz, DMSO-d6) d = 9.62 (s, 8H), 4.05 (br,
16H), 3.80 (br, 16 H), 3.61 (s, 24H), 3.25 (br, 32H),
1.35 (s, 48H). 13C NMR d = 162.98, 154.77, 153.55,
137.59, 58.75, 56.70, 47.59, 26.59, 8.57. UV/Vis (H2O):
kmax (loge) = 354 (3.9), 657 nm (4.0).
1
was treated according to 5.1.5. Yield: 22 mg (85%). H
NMR (300 MHz, DMSO-d6) d = 9.36 (br, 4H), 8.98
(br, 4H), 7.97 (br, 4 H), 5.11(br, 8H), 4.15 (br, 8H),
3.42 (br, 36H). 13C NMR d = 160.37, 148.33, 137.85,
129.71, 124.47, 119.69, 107.05, 65.15, 63.78, 54.26. UV/
4.6.10. Octakis (N,N,N-diethyl-methyl-2-aminoethyl sul-
fanyl)phthalocyanine zinc octaiodine (10).16 Compound