PREDOMINANT EFFECT OF CONNECTING ATOM AND POSITION OF SUBSTITUENTS ON AZOMETHINE
5
1
6 H, CH CH CH ), 1.12 (h, J = 7 Hz, 16H, CH CH ),
1,4,8,11,15,18,22,25-Octakis(butyloxy)phthalocy-
aninato zinc(II) (aO). Compound aO was prepared
according to the general procedure described above
starting from aO-H (100 mg, 0.092 mmol) and zinc
acetate (118 mg, 0.64 mmol). Eluent for column
2
2
3
2
3
13
0
.61 (t, J = 7 Hz, 24H, CH ), -0.36 (s, 2H, NH). C NMR
3
(125 MHz, CDCl /pyridine-d 3:1): d, ppm 139.0, 131.0,
3
5
32.9, 31.8, 30.5, 23.1 and 14.3 (some aromatic signals
-1
were not detected). IR (ATR): n, cm 3297 (NH), 2955,
2
1
1
928, 2857, 1570, 1457, 1376, 1323, 1311, 1188,
146, 1093, 1066, 1025 and 875. MS (MALDI): m/z
074.8 [M] .
chromatography chloroform/THF 10:1. Yield 102 mg
1
of green solid (95%). H NMR (500 MHz, CDCl /
3
+
pyridine-d 3:1):d, ppm7.32(s, 8H,ArH), 4.64(t,J=8Hz,
5
2
,3,9,10,16,17,23,24-Octakis(butyloxy)phthalo-
16H, OCH ), 1.98 (p, J = 8 Hz, 16H, OCH CH ), 1.39
2
2
2
cyanine (bO-H). Compound bO-H was prepared accor-
ding to the general procedure described above starting
from 5 (400 mg, 1.47 mmol) and metal lithium (72
mg, 10.3 mmol). Eluent for column chromatography
toluene/chloroform/THF 20:20:1 (R = 0.4). Yield 118
mg of green solid (29%). H NMR (300 MHz, CDCl /
(h, J = 8 Hz, 16 H, CH CH ), 0.81 (t, J = 7 Hz, 24 H,
2
3
13
CH3). C NMR (125 MHz, CDCl /pyridine-d 3:1): d,
ppm 151.1, 128.1, 116.8, 71.3, 31.7, 19.6 and 14.3. IR
(ATR): n, cm 2959, 2932, 2871, 1596, 1498, 1467,
1377, 1311, 1256, 1199, 1094, 1065, 1039, 946 and 895.
3
5
-1
f
1
+
MS (MALDI): m/z 1152.5 [M] . The analytical data
3
pyridine-d 3:1): d, ppm 7.72–7.20 (br s, 8H, ArH,
corresponded well with those published [27].
5
partially overlapped by a signal of solvent), 4.12 (br s,
1,4,8,11,15,18,22,25-Octakis(pentyl)phthalocy-
aninato zinc(II) (aC). Compound aC was prepared
according to the general procedure described above
starting from aC-H (53 mg, 0.049 mmol) and zinc
acetate (253 mg, 1.38 mmol). Eluent for column
chromatography hexane/chloroform/THF 100:20:1.Yield
1
6H, OCH ), 2.20–2.07 (m, 16H, OCH CH ), 1.88 (hept,
2
2
2
J = 7 Hz, 16H, CH CH ) and 1.33 (t, J = 7 Hz, 24H, CH ).
2
3
3
1
3
C NMR (75 MHz, CDCl /pyridine-d 3:1): d, ppm
8.62, 32.00, 19.84 and 14.48 (aromatic signals were
not detected). IR (ATR): n, cm 3295 (NH), 2959, 2929,
3
5
6
-
1
1
2
1
873, 1608, 1491, 1451, 1384, 1330, 1278, 1231, 1199,
100, 1072, 1027, 970, 880 and 856. Elemental analysis
30 mg of green solid (53%). H NMR (500 MHz,
CDCl /pyridine-d 3:1): d, ppm 7.64 (s, 8H, ArH), 4.37
3
5
calcd. for C H N O × 1H O (%): C 69.29, H 7.63, N
(s, 16H, CH CH CH CH CH ), 1.96 (p, J = 8 Hz, 16H,
6
4
82
8
8
2
2
2
2
2
3
1
0.10; found C 69.13, H 7.81, N 10.09. UV-vis (THF):
CH CH CH CH ), 1.37 (p, J = 8 Hz, 16H, CH CH CH ),
2
2
2
3
2
2
3
-
1
-1
lmax, nm (e, M .cm ) 697 (194 550), 660 (157 060), 645
57 300), 599 (30 670), 424sh and 347 (93 660). This
compound has been prepared by similar method [25].
,3,9,10,16,17,23,24-Octakis(pentyl)phthalocy-
1.13 (h, J = 7 Hz, 16H, CH CH ), 0.60 (t, J = 7 Hz, 24H,
13
2
3
(
CH3). C NMR (125 MHz, CDCl /pyridine-d 3:1):
3 5
d, ppm 154.1, 138.6, 130.2, 32.9, 31.7, 30.8, 23.2 and
2
14.3 (signal of one aromatic carbon was not detected).
-1
anine (bC-H). Compound bC-H was prepared according
to the general procedure described above starting from
IR (ATR): n, cm 2955, 2926, 2870, 2856, 1600, 1466,
1373, 1322, 1293, 1167, 1094, 995 and 891. UV-vis
-1
-1
8
(128 mg, 0.48 mmol) and metal lithium (24 mg, 3.46
(THF): lmax, nm (e, M .cm ) 700 (217 700), 666sh, 632
1
+
mmol). Yield 36 mg of green solid (28%). H NMR
500 MHz, CDCl /pyridine-d 3:1): d, ppm 8.88 (s, 8H,
(38 200), 351 (52 900). MS (MALDI): m/z 1136.7 [M] .
(
2,3,9,10,16,17,23,24-Octakis(butyloxy)phthalocy-
aninato zinc(II) (bO). Compound bO was prepared
according to the general procedure described above
starting from bO-H (105 mg, 0.096 mmol) and zinc
acetate (123 mg, 0.67 mmol). Eluent for column
3
5
ArH), 3.04–2.84 (m, 16H, CH CH CH CH CH ), 1.85–
2
2
2
2
3
1
.72 (m, 16 H, CH CH CH CH ), 1.47–1.38 (m, 16 H,
2 2 2 3
CH CH CH ), 1.37–1.27 (m, 16H, CH CH ), 0.86–0.76
2
2
3
2
3
1
3
(
m, 24H, CH ), -0.13 (s, 2H, NH). C NMR (125 MHz,
3
CDCl /pyridine-d 3:1): d, ppm 34.2, 32.6, 23.0 and 14.4
chromatography toluene/chloroform/THF 20:5:1 (R =
3
5
f
-1
1
(
some of the signals were not detected). IR (ATR): n, cm
0.7). Yield 79 mg of green solid (71%). H NMR (300
3
1
1
292 (NH), 2956, 2929, 2867, 1647, 1506, 1458, 1376,
MHz, CDCl /pyridine-d 3:1): d, ppm 8.84 (s, 8H, ArH),
3
5
340, 1324, 1104, 1016 and 893. MS (MALDI): m/z
4.44 (t, J = 6 Hz, 16H, OCH ), 2.10–1.96 (m, 16H,
2
+
074.8 [M] . This compound has been already prepared
OCH CH ), 1.69 (hept, J = 7 Hz, 16H, CH CH ), 1.09
2
2
2
3
1
3
but characterized by MS only [26].
(t, J = 7 Hz, 24H, CH3). C NMR (75 MHz, CDCl3/
pyridine-d 3:1): d, ppm 152.97, 151.37, 132.25, 105.74,
5
-1
6
2
9.15, 31.59, 19.49 and 14.02. IR (ATR): n, cm 2960,
General procedure for synthesis of zinc Pcs
938, 2873, 1603, 1494, 1457, 1414, 1386, 1351, 1275,
Corresponding metal-free Pc and anhydrous zinc
acetateweredissolvedinamixtureofpyridine/chloroform
1233, 1199, 1103, 1075, 1047, 970, 899 and 857. UV-vis
-1
-1
(THF): lmax, nm (e, M .cm ) 672 (345 500), 643 (47
3
:1 (3 mL) to obtain homogenous solution. This solution
600), 607 (50 500), 425sh a 355 nm (121 800). MS
+
was refluxed for 1 h, solvents were evaporated to dryness,
and dissolved again in THF (2 mL). Water (20 mL) was
then added, dark precipitate was collected by filtration,
washed with water and dried. Crude product was purified
by column chromatography on silica (mobile phases are
mentioned for each compound below).
(MALDI): m/z 1152.4 [M] . This compound has been
already prepared by similar method [25].
2,3,9,10,16,17,23,24-Octakis(pentyl)phthalocy-
aninato zinc(II) (bC). Compound bC was prepared
according to the general procedure described above
starting from bC-H (28 mg, 0.026 mmol) and zinc acetate
Copyright © 2016 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2016; 20: 5–12