3508 J. Phys. Chem. A, Vol. 107, No. 18, 2003
Cheng et al.
(Al2O3 III, CH2Cl2), rechromatographed (BioBeads S-X4,
toluene), vacuum-dried (∼60 °C), and weighed (56 mg, 78%).
UV-vis (toluene, 2.0 µM) λmax, nm (ꢀ, M-1 cm-1): 741 (2.9
× 105). NMR (C6D6): δ 7.58 (m, 1,4-Ar H), 6.95 (m, 2,3-Ar
H), 6.77 (s, 5,44-CH), 5.40 (t, OR-1 CH2), 2.44 (m, OR-2 CH2),
1.80 (m, OR-3 CH2), 1.23 (t, OR CH3), 0.43 (m, SiR-5 CH2;
SiR CH3), 0.18 (m, SiR-4 CH2), 0.00 (m, SiR-3 CH2), -0.91
(m, SiR-2 CH2), -2.06 (m, SiR-1 CH2). MS-HRFAB exact
mass m/z: calc for C156H190N8O10Si3 (M)+, 2419.3912; found,
2419.3959, 2419.3855.
H2Pc(dib)4(OiBu)8, Pc 150, 21. Under Ar, a refluxing solution
of 9,10-dihydro-1,4-di(2-methyl-1-propoxy)-9,10[1′,2′]-ben-
zenoanthracene-2,3-dicarbonitrile (200 mg) and 2-methyl-1-
propanol (18 mL) was treated with Li (shot, 20 mg), refluxed
for 3 h, and treated with H2O (20 mL). The mixture was
extracted with toluene (3 times, 100 mL each time), and the
extracts were combined, dried (Na2SO4), filtered, and evaporated
to dryness by rotary evaporation (∼30 °C). The solid was
washed (CH3OH), chromatographed (silica gel, toluene), vacuum-
dried (room temperature), and weighed (50 mg, 25%). UV-
vis (toluene) λmax, nm: 737, 764. NMR (C6D6): δ 7.63 (m,
1,4-Ar H), 6.98 (m, 2,3-Ar H), 6.84 (s, 5,44-CH), 4.92 (d OR-1
CH2), 2.85 (m, OR-2 CH), 1.35 (d, OR CH3), 0.01 (s, NH).
MS-HRFAB exact mass, m/z: calc for C120H115N8O8 (M +
H)+, 1795.8838; found, 1795.8774, 1795.8745.
The compound is a green solid. It is soluble in CH2C12,
toluene, and hexanes.
SiPc(dib)4(OnBu)8[OSi(i-C4H9)2(n-C18H37)]2, Pc 171, 18.
Under Ar, a mixture of SiPc(dib)4(OnBu)8[OH]2 (50 mg), (i-
C4H9)2(n-C18H37)SiCl30 (500 µL), pyridine (8 mL), and toluene
(50 mL) was refluxed for 6 h and evaporated to dryness by
rotary evaporation (∼45 °C). The solid was dissolved in pentane
(25 mL), and the solution was filtered and evaporated to dryness
by rotary evaporation (∼45 °C). The resulting solid was
chromatographed (Al2O3 III, hexanes-toluene solution), re-
chromatographed (BioBeads S-X4, toluene), vacuum-dried
(∼60 °C), and weighed (53 mg, 74%). UV-vis (toluene, 2.2
µM) λmax, nm (ꢀ, M-1 cm-1): 745 (2.7 × 105). NMR (C6D6):
δ 7.57 (m, 1,4-Ar H), 6.93 (m, 2,3-Ar H), 6.78 (s, 5,44-CH),
5.40 (t, OR-1 CH2), 2.47 (m, OR-2 CH2), 1.78 (m, OR-3 CH2),
1.22 (t, OR CH3), 1.2-1.4 (m, SiRod-7-17 CH2), 0.90 (t, SiRod
CH3), 0.54 (m, SiRod-6 CH2), 0.52 (m, SiRod-5 CH2), 0.29 (m,
SiRod-4 CH2), 0.10 (m, SiRod-3 CH2), -0.58 (m, SiRb CH; SiRb
CH3), -0.92 (m, SiRod-2 CH2), -2.00 (m, SiRod-1 CH2), -2.14
(d, SiRb CH2). MS-HRFAB exact mass, m/z: calc for
The compound is a green solid. It is slightly soluble in CH2-
C12 and toluene, and insoluble in hexanes.
SiPc(dib)4(OiBu)8[OH]2, Pc 151, 22. A mixture of H2Pc(dib)4-
(OiBu)8 (82 mg), HSiCl3 (1.2 mL), toluene (40 mL), CH3CN
(40 mL), CH2Cl2 (60 mL), and (n-C3H7)3N (8 mL) was stirred
for 5 days, treated with a stream of Ar, and then evaporated to
dryness by rotary evaporation (∼30 °C). The solid was stirred
with toluene (50 mL), CH2Cl2 (50 mL), (n-C3H7)3N (10 mL),
and aqueous NaHCO3 (saturated, 120 mL), and the mixture was
extracted with toluene (4 times, 200 mL each time). The extracts
were combined, dried (Na2SO4), and evaporated to dryness by
rotary evaporation (∼30 °C), and the solid was chromatographed
(silica gel, toluene-ethyl acetate solution), vacuum-dried (room
temperature), and weighed (34 mg, 41%). UV-vis (toluene)
λmax, nm: 750. NMR (C6D6): δ 7.65 (m, 1,4-Ar H), 7.01 (m,
C
172H222N8O10Si3 (M)+, 2643.6416; found, 2643.6449, 2643.6330.
The compound is a green solid. It is soluble in CH2C12,
2,3-Ar H), 6.82 (s, 5,44-CH), 4.77 (d, OR-1 CH2), 2.83 (m,
OR-2 CH), 1.35 (d, OR CH3).
toluene, and hexanes.
The solid is a green solid. It is soluble in CH2C12 and toluene
and insoluble in hexanes.
SiPc(dib)4(OnBu)8[OSi8O12(C5H9)7]2, Pc 144, 19. Under Ar,
a mixture of SiPc(dib)4(OnBu)8[OH]2 (12 mg), 3,5,7,9,11,13,-
15-heptacyclopentylpentacyclo[9.5.1.1.3,91.5,1517,13]octasiloxan-
1-ol ((C5H9)7Si8O12OH; 300 mg), and pyridine (15 mL) was
slowly distilled for 7 h (8 mL distillate) and evaporated to
dryness by rotary evaporation (∼30 °C). The solid was
chromatographed twice (silica gel, cyclohexane-CH2Cl2 solu-
tion), rechromatographed (Al2O3 III, cyclohexane-CH2Cl2 solu-
tion), vacuum-dried (room temperature), and weighed (15 mg,
63%). UV-vis (toluene, 4.9 µM) λmax, nm (ꢀ, M-1 cm-1): 748
(2.8 × 105). NMR (pyridine- d5): δ 7.89 (m, 1,4-Ar H), 7.28
(m, 2,3-Ar H), 6.88 (s, 5,44-CH), 4.99 (m, OR-1 CH2), 2.60
(m, OR-2 CH2), 2.21 (m, OR-3 CH2), 1.54 (t, OR CH3), -1.45
to-0.22(m,C5H9CH2).MS-MALDI,m/z: calcforC190H239N8O34-
Si17 (M + H)+, 3656; found, 3652.
SiPc(dib)4(OiBu)8[OSi(n-C6H13)3]2, Pc 142, 23. Under Ar, a
mixture of SiPc(dib)4(OiBu)8[OH]2 (7 mg), (n-C6H13)3SiCl (60
mg), pyridine (1 mL) and toluene (4 mL) was refluxed for 2 h
and evaporated to dryness by rotary evaporation (∼30 °C). The
solid was chromatographed (Al2O3 III, hexanes-CH2Cl2 solu-
tion), rechromatographed (Bio Beads S-X3, toluene), again
rechromatographed (silica gel, hexanes-CH2Cl2 solution),
vacuum-dried (room temperature), and weighed (4 mg, 44%).
UV-vis (toluene) λmax, nm: 748. NMR (C6D6): δ 7.59 (m,
1,4-Ar H), 6.95 (m, 2,3-Ar H), 6.82 (s, 5,44-CH), 5.12 (m, OR-1
CH2), 2.94 (m, OR-2 CH), 1.46 (d, OR CH3), 0.39 (m, SiR-5
CH2; SiR CH3), 0.15 (m, SiR-4 CH2), 0.01 (m, SiR-3 CH2),
-0.88 (m, SiR-2 CH2), -2.02 (m, SiR-1 CH2). MS-HRFAB
exact mass, m/z: calc for C156H191N8O10 Si3 (M + H)+,
2420.3913; found, 2420.3875, 2420.3937.
The compound is a green solid. It is soluble in CH2Cl2 and
toluene, and slightly soluble in hexanes.
The compound is a green solid. It is soluble CH2C12, toluene,
and hexanes.
9,10-Dihydro-1,4-di(2-methyl-1-propoxy)-9,10[1′,2′]-ben-
zenoanthracene-2,3-dicarbonitrile, 20. Under Ar, a mixture of
9,10-dihydro-1,4-dihydroxy-9,10[1′,2′]-benzenoanthracene-2,3-
dicarbonitrile (200 mg), 9, 1-iodo-2-methylpropane (2 mL),
K2CO3 (1.2 g), and acetone (12 mL) was refluxed for 14 h and
evaporated to dryness by rotary evaporation (∼30 °C). The solid
was extracted into CH2Cl2 (50 mL), recovered by rotary evap-
oration (∼30 °C) after the extract had been filtered, chromato-
graphed (Al2O3 III, toluene), vacuum-dried (room temperature),
and weighed (230 mg, 86%). NMR (CDC13): δ 7.43 (m,
5,8,3′,6′-Ar H), 7.08 (m, 6,7,4′,5′-Ar H), 5.85 (s, 9,10-CH), 3.96
(d, OR-1 CH2), 2.29 (m, OR-2 CH), 1.22 (d, OR CH3).
The compound is a light-yellow solid. It is soluble in CH2-
Cl2 and toluene, and insoluble in hexanes.
SiPc(dib)4(OiBu)8[OSi8O12(C5H9)7]2, Pc 143, 24. Under Ar,
a mixture of SiPc(dib)4(OiBu)8[OH]2 (12 mg), (C5H9)7Si8O12-
OH (300 mg), and pyridine (15 mL) was slowly distilled for 6
h (8 mL distillate) and evaporated to dryness by rotary
evaporation (∼30 °C). The solid was chromatographed twice
(silica gel, cyclohexane-toluene solution), rechromatographed
twice (Bio Beads S-X1, toluene), vacuum-dried (room tem-
perature), and weighed (15 mg, 63%). UV-vis (toluene, 2.9
µM) λmax, nm (ꢀ, M-1 cm-1): 749 (2.6 × 105). NMR (pyridine-
d5): δ 7.88 (m, 1,4-Ar H), 7.26 (m, 2,3-Ar H), 6.92 (s, 5,44-
CH), 3.07 (m, OR-2 CH), 1.65 (d, OR CH3), 1.45 to -0.05 (m,
C5H9CH2). MS-MALDI, m/z: calc for C190H239N8O34Si17 (M
+ H)+, 3656; found 3656.