Photophysical Properties of Substituted Phthalocyanines
J. Am. Chem. Soc., Vol. 119, No. 26, 1997 6031
Torr), and weighed (5 mg, 1% of weight of H2N4-xPx(OBu)8). UV-
1,4,17,20-OR-3 CH2), 1.11 (t, 8,13,24,29-OR CH3), 0.95 (t, 1,4,17,-
20-OR CH3). 13C NMR (C6D6): δ 152.20 (1,4,17,20-Ar C; 5,16,20,-
32-Ar C), 150.72 (7,14,23,30-Ar C; 8,13,24,29-Ar C), 131.89 (8a,-
12a,24a,28a-Ar C), 127.36 (10,11,26,27-Ar C), 127.17 (4a,16a,20a,32a-
Ar C), 126.15 (7a,13a,23a,29a-Ar C), 125.02 (9,12,25,28-Ar C), 118.32
(2,3,18,19-Ar C), 77.42 (8,13,24,29-OR-1 C), 72.37 (1,4,17,20-OR-1
C), 33.65 (8,13,24,29-OR-2 C), 32.35 (1,4,17,20-OR-2 C), 20.10 (1,4,-
17,20-OR-3 C; 8,13,24,29-OR-3 C), 14.46 (1,4,17,20-OR-4 C; 8,13,-
24,29-OR-4 C). MS-HRFAB exact mass, m/z: calcd for C72H86N8O8
(M + H)+, 1191.6647; found, 1191.6632, 1191.6592.
1
vis (λmax (nm), ꢀ (M-1 cm-1)) (toluene, 2.1 mM): 862, 2.0 × 105. H
NMR (C6D6): δ 9.23 (m, 1,4,10,13,19,22,28,31-Ar H), 7.68 (m, 2,3,-
11,12,20,21,29,30-Ar H), 5.40 (t, OR-1 CH2), 2.38 (m, OR-2 CH2),
2.27 (s, NH), 1.67 (m, OR-3 CH2), 1.03 (t, OR CH3). 13C NMR
(C6D6): δ 150.59 (5,9,14,18,23,27,32,36-Ar C; 6,8,15,17,24,26,33,35-
Ar C), 131.54 (4a,9a,13a,18a,22a,27a,31a,36a-Ar C), 127.60 (2,3,11,-
12,20,21,29,30-Ar C), 124.91 (1,4,10,13,19,22,28,31-Ar C), 123.51
(5a,8a,14a,17a,23a,26a,32a,35a-Ar C), 77.24 (OR-1 C), 33.34 (OR-2
C), 20.07 (OR-3 C), 14.49 (OR-4 C).
The compound is a brown solid. It is soluble in toluene, CH2Cl2,
and pyridine and slightly soluble in hexane.
The compound is a brown solid. It is soluble in toluene, CH2Cl2,
and pyridine and slightly soluble in hexane.
H2N1P3(OBu)8. The chromatography of the H2N4-xPx(OBu)8 was
continued further yet (toluene/ethyl acetate, 1:1), and the fraction
isolated was treated as before (102 mg, 17% of weight of
H2N4-xPx(OBu)8). UV-vis (λmax (nm), ꢀ (M-1 cm-1)) (toluene, 1.5
µM): 756, 0.82 × 105; 802, 0.66 × 105. 1H NMR (C6D6): δ 9.22 (m,
23,26-Ar H), 7.68 (m, 24,25-Ar H), 7.56 (d, 2,17-Ar H), 7.51 (s, 9,-
10-Ar H), 7.43 (d, 3,16-Ar H), 5.45 (t, 22,27-OR-1 CH2), 4.94 (m,
1,18-OR-1 CH2; 4,15-OR-1 CH2), 4.70 (t, 8,11-OR-1 CH2), 2.30 (m,
22,27-OR-2 CH2), 2.21 (m, 1,18-OR-2 CH2; 4,15-OR-2 CH2; 8,11-
OR-2 CH2), 1.78 (m, 22,27-OR-3 CH2), 1.75 (m, 1,18-OR-3 CH2; 4,-
15-OR-3 CH2; 8,11-OR-3 CH2), 1.18 (t, 22,27-OR CH3), 1.13 (t, 1,18-
OR CH3; 4,15-OR CH3), 0.93 (t, 8,11-OR CH3), 0.63 (s, NH). 13C
NMR (C6D6): δ 152.62 (21,28-Ar C), 152.41 (1,18-Ar C; 4,15-Ar C;
5,14-Ar C; 7,12-Ar C; 8,11-Ar C; 19,30-Ar C), 150.73 (22,27-Ar C),
132.02 (22a,26a-Ar C), 129.84 (7a,11a-Ar C), 127.35 (24,25-Ar C),
126.04 (21a,27a-Ar C), 125.30 (4a,14a-Ar C; 18a,30a-Ar C), 125.05
(23,26-Ar C), 120.36 (2,17-Ar C), 120.05 (3,16-Ar C), 118.05 (9,10-
Ar C), 77.50 (22,27-OR-1 C), 73.00 (1,18-OR-1 C; 4,15-OR-1 C), 72.22
(8,11-OR-1 C), 33.63 (22,27-OR-2 C), 32.57 (1,18-OR-2 C), 32.47
(4,15-OR-2 C), 32.35 (8,11-OR-2 C), 20.07 (1,18-OR-3 C; 22,27-OR-3
C), 19.99 (4,15-OR-3 C; 8,11-OR-3 C), 14.39 (1,18-OR-4 C; 4,15-
OR-4 C; 8,11-OR-4 C; 22,27-OR-4 C). MS-HRFAB exact mass, m/z:
calcd for C68H84N8O8 (M + H)+, 1141.6490; found, 1141.6453,
1141.6449.
H2N3P1(OBu)8. The chromatography of the H2N4-xPx(OBu)8 was
continued (toluene). The fraction isolated was treated in the same way
as the first one (34 mg, 6% of weight of H2N4-xPx(OBu)8). UV-vis
(λmax (nm), ꢀ (M-1 cm-1)) (toluene, 1.9 µM): 814, 0.99 × 105; 851,
0.89 × 105. 1H NMR (C6D6): δ 9.23 (m, 1,4-Ar H; 10,29-Ar H; 13,-
26-Ar H), 7.69 (m, 2,3-Ar H; 11,28-Ar H; 12,27-Ar H), 7.44 (s, 19,-
20-Ar H), 5.55 (t, 5,34-OR-1 CH2), 5.39 (t, 9,30-OR-1 CH2), 5.31 (t,
14,25-OR-1 CH2), 4.75 (t, 18,21-OR-1 CH2), 2.34 (m, 5,34-OR-2 CH2;
9,30-OR-2 CH2), 2.24 (m, 14,25-OR-2 CH2; 18,21-OR-2 CH2), 1.91
(s, NH), 1.85 (m, 5,34-OR-3 CH2; 9,30-OR-3 CH2), 1.66 (m, 14,25-
OR-3 CH2; 18,21-OR-3 CH2), 1.13 (t, 5,34-OR CH3), 1.02 (m, 9,30-
OR CH3; 14,25-OR CH3), 0.96 (t, 18,21-OR CH3). 13C NMR (C6D6):
δ 152.22 (17,22-Ar C), 151.50 (18,21-Ar C), 150.63 (5,34-Ar C; 6,-
33-Ar C), 149.99 (8,31-Ar C; 9,30-Ar C; 14,25-Ar C; 15,24-Ar C),
131.97 (4a,34a-Ar C), 131.67 (9a,29a-Ar C; 13a,25a-Ar C), 127.73
(17a,21a-Ar C), 127.53 (2,3-Ar C), 127.41 (11,28-Ar C; 12,27-Ar C),
125.69 (1,4-Ar C), 124.91 (10,29-Ar C; 13,26-Ar C), 121.42 (5a,33a-
Ar C; 8a,30a-Ar C; 14a,24a-Ar C), 117.28 (19,20-Ar C), 77.35 (5,34-
OR-1 C; 9,30-OR-1 C), 77.27 (14,25-OR-1 C), 72.23 (18,21-OR-1 C),
33.67 (5,34-OR-2 C), 33.31 (9,30-OR-2 C; 14,25-OR-2 C), 32.37 (18,-
21-OR-2 C), 20.33 (5,34-OR-3 C), 20.12 (9,30-OR-3 C; 14,25-OR-3
C), 20.03 (18,21-OR-3 C), 14.46 (5,34-OR-4 C; 9,30-OR-4 C; 14,25-
OR-4 C; 18,21-OR-4 C). MS-HRFAB exact mass, m/z: calcd for
C76H88N8O8 (M + H)+, 1241.6803; found, 1241.6807, 1241.6795.
The compound is a brown solid. It is soluble in toluene, CH2Cl2,
and pyridine and slightly soluble in hexane.
The compound is a dark-green solid. It is soluble in toluene, CH2-
Cl2, and pyridine and slightly soluble in hexane.
H2N0P4(OBu)8 (H2Pc(OBu)8).26,28,29 The chromatography of the
H2N4-xPx(OBu)8 was continued yet again (ethyl acetate), and the fraction
separated was treated as before (30 mg, 5% of weight of
H2N4-xPx(OBu)8). UV-vis (λmax (nm), ꢀ (M-1 cm-1)) (toluene, 2.1
µM): 739, 0.95 × 105; 761, 1.1 × 105. 1H NMR (C6D6): δ 7.53 (s,
Ar H), 4.91 (t, OR-1 CH2), 2.20 (m, OR-2 CH2), 1.72 (m, OR-3 CH2),
1.04 (t, OR CH3), -0.28 (s, NH). 13C NMR (C6D6): δ 152.63 (5,7,-
12,14,19,21,26,28-Ar C), 149.20 (1,4,8,11,15,18,22,25-Ar C), 127.75
(4a,7a,11a,14a,18a,21a,25a,28a-Ar C), 120.33 (2,3,9,10,16,17,23,24-
Ar C), 73.01 (OR-1 C), 32.51 (OR-2 C), 19.98 (OR-3 C), 14.37 (OR-4
C).
c-H2N2P2(OBu)8. The chromatography of the H2N4-xPx(OBu)8 was
continued further (toluene/CH2Cl2, 1:1). The fraction separated was
treated in the same way as the previous two fractions (62 mg, 10% of
weight of H2N4-xPx(OBu)8). UV-vis (λmax (nm), ꢀ (M-1 cm-1))
(toluene, 2.2 µM): 807, 1.9 × 105. 1H NMR (C6D6): δ 9.21 (m, 1,-
27-Ar H; 4,24-Ar H), 7.67 (m, 2,26-Ar H; 3,25-Ar H), 7.52 (d, 10,-
18-Ar H), 7.40 (d, 11,17-Ar H), 5.51 (t, 28,32-OR-1 CH2), 5.30 (t,
5,23-OR-1 CH2), 4.95 (t, 9,19-OR-1 CH2), 4.71 (t, 12,16-OR-1 CH2),
2.31 (m, 5,23-OR-2 CH2; 28,32-OR-2 CH2), 2.20 (m, 9,19-OR-2 CH2;
12,16-OR-2 CH2), 1.80 (m, 5,23-OR-3 CH2; 28,32-OR-3 CH2), 1.62
(m, 9,19-OR-3 CH2; 12,16-OR-3 CH2), 1.54 (s, NH), 1.10 (t, 28,32-
OR CH3), 1.06 (t, 5,23-OR CH3), 1.00 (t, 9,19-OR CH3), 0.94 (t, 12,-
16-OR CH3). 13C NMR (C6D6): δ 152.38 (13,15-Ar C), 152.20 (8,20-
Ar C; 9,19-Ar C; 12,16-Ar C), 150.70 (6,22-Ar C; 29,31-Ar C), 150.33
(5,23-Ar C; 28,32-Ar C), 131.98 (27a,32a-Ar C), 131.21 (4a,23a-Ar
C), 126.85 (8a,19a-Ar C; 12a,15a-Ar C), 127.75 (2,26-Ar C; 3,25-Ar
C), 125.01 (1,27-Ar C), 124.92 (4,24-Ar C), 123.71 (5a,22a-Ar C),
123.11 (28a,31a-Ar C), 119.89 (10,18-Ar C), 117.59 (11,17-Ar C),
77.50 (28,32-OR-1 C), 77.29 (5,23-OR-1 C), 72.98 (9,19-OR-1 C),
72.16 (12,16-OR-1 C), 33.61 (28,32-OR-2 C), 33.29 (5,23-OR-2 C),
32.53 (9,19-OR-2 C), 32.38 (12,16-OR-2 C), 20.09 (5,23-OR-3 C; 28,-
32-OR-3 C), 20.01 (9,19-OR-3 C; 12,16-OR-3 C), 14.44 (5,23-OR-4
C; 9,19-OR-4 C; 12,16-OR-4-C; 28,32-OR-4 C). MS-HRFAB exact
mass, m/z: calcd for C72H86N8O8 (M + H)+, 1191.6647; found,
1191.6677, 1191.6598.
The compound is a green solid. It is soluble in toluene, CH2Cl2,
and pyridine and slightly soluble in hexane.
SiN4P0(OBu)8(OH)2 (SiNc(OBu)8(OH)2). SiN4P0(OBu)8(OH)2 was
prepared by the same type of procedure used for the synthesis of
c-SiN2P2(OBu)8(OH)2 (route 1, see below) (78%). UV-vis (λmax (nm),
toluene): 865. 1H NMR (C6D6): δ 9.23 (m, 1,4,10,13,19,22,28,31-
Ar H), 7.68 (m, 2,3,11,12,20,21,29,30-Ar H), 5.35 (t, OR-1 CH2), 2.35
(m, OR-2 CH2), 1.65 (m, OR-3 CH2), 1.03 (t, OR CH3), -3.79 (s, br,
OH). 13C NMR (C6D6): δ 150.98 (6,8,15,17,24,26,33,35-Ar C), 148.37
(5,9,14,18,23,27,32,36-Ar C), 131.63 (4a,9a,13a,18a,22a,27a,31a,36a-
Ar C), 127.73 (2,3,11,12,20,21,29,30-Ar C), 124.84 (1,4,10,13,19,22,-
28,31-Ar C), 122.71 (5a,8a,14a,17a,23a,26a,32a,35a-Ar C), 77.47 (OR-1
C), 33.40 (OR-2 C), 19.98 (OR-3 C), 14.48 (OR-4 C).
The compound is a brown solid. It is soluble in toluene, CH2Cl2,
and pyridine, and slightly soluble in hexane. Its crystals are acicular.
SiN3P1(OBu)8(OH)2. SiN3P1(OBu)8(OH)2 was prepared by route 1
(56%). UV-vis (λmax (nm), toluene): 825; 861. 1H NMR (C6D6): δ
9.22 (m, 1,4-Ar H; 10,29-Ar H; 13,26-Ar H), 7.64 (m, 2,3-Ar H; 11,-
28-Ar H; 12,27-Ar H), 7.45 (s, 19,20-Ar H), 5.54 (t, 5,34-OR-1 CH2),
5.36 (t, 9,30-OR-1 CH2), 5.30 (t, 14,25-OR-1 CH2), 4.75 (t, 18,21-
The compound is a dark-green solid. It is soluble in toluene, CH2-
Cl2, and pyridine and slightly soluble in hexane.
t-H2N2P2(OBu)8. The chromatography of the H2N4-xPx(OBu)8 was
continued still further (CH2Cl2), and the resulting fraction was treated
as before (12 mg, 2% of weight of H2N4-xPx(OBu)8). UV-vis (λmax
(nm), ꢀ (M-1 cm-1)) (toluene, 1.7 µM): 750, 0.98 × 105; 852, 0.75 ×
105. 1H NMR (C6D6): δ 9.23 (m, 9,12,25,28-Ar H), 7.69 (m, 10,11,-
26,27-Ar H), 7.47 (s, 2,3,18,19-Ar H), 5.48 (t, 8,13,24,29-OR-1 CH2),
4.75 (t, 1,4,17,20-OR-1 CH2), 2.32 (m, 8,13,24,29-OR-2 CH2), 2.22
(m, 1,4,17,20-OR-2 CH2), 1.83 (m, 8,13,24,29-OR-3 CH2), 1.60 (m,
(28) Ford, W. E.; Rihter, B. D.; Kenney, M. E.; Rodgers, M. A. J.
Photochem. Photobiol. 1989, 50, 277.
(29) Rihter, B. D.; Kenney, M. E.; Ford, W. E.; Rodgers, M. A. J. J.
Am. Chem. Soc. 1990, 112, 8064.