S. Choi et al.
DyesandPigments163(2019)381–392
123.18, 127.60, 130.36, 131.27, 133.45, 134.75, 135.64, 148.10,
149.50, 162.96; MALDI–TOF MS: m/z 904.11 (100%, [M + 2Na]+);
Elemental analysis: Calcd for C36H14Br2N2Na2O10S2: C, 47.81; H, 1.56;
N, 3.10; S, 7.09%. Found: C, 48.66; H, 1.51; N, 3.08; S, 7.25.
2.2.9. N,N′-Bis(2,6-diisopropylphenyl)-1,7-diphenoxyperylene-3,4,9,10-
tetracarboxydiimide
N,N′-Bis(2,6-diisopropylphenyl)-1,7-dibromoperylene-3,4,9,10-tet-
racarboxydiimide (28.66 g, 0.033 mol) was suspended in 800 mL of
NMP with phenol (15.53 g, 0.165 mol) The mixture was stirred under
N2 atmosphere. The temperature was raised to 120 °C and half of an-
hydrous K2CO3 (10.36 g, 0.075 mol) was suspended in the mixture.
After 30 min, the other half of K2CO3 (10.36 g, 0.075 mol) was added.
The reaction was completed by stirring at 120 °C overnight then cooled
to room temperature. The mixture was slowly poured into 5000 mL of
5% HCl solution. A precipitate was then collected by suction filtration,
repeatedly washed with distilled water. Crude product was dried in
vacuum oven at 80 °C overnight. The product was purified by column
chromatography on silica gel using DCM as the eluent. Yield: 82.8%
2.2.5. N,N'-Bis-[4-(sulfuric acid)phenyl]-3,4,9,10-perylenebis(dicarboximide)
A mixture of perylene-3,4,9,10- tetracarboxylic dianhydride (20 g,
0.051 mol), sulfanilic acid (17.32 g, 0.10 mol), m-cresol (400 ml) and
isoquinoline (30 ml) was stirred at 50 °C overnight. The solution was
heated at 130 °C under a nitrogen atmosphere. When the temperature is
raised to 130 °C, turned off the nitrogen gas. After 5 h reaction at
130 °C, the temperature was raised to 150 °C and kept for 4 h. The re-
action was then completed by stirring at 200 °C overnight. The warm
solution was poured into 300 ml of acetone, and the precipitate was
filtered out and dried at 100 °C under vacuum for 2 h. The crude pro-
duct was washed with 5% NaOH until the characteristic green fluor-
escent colour of perylene dianhydride disappear and the unreacted 4-
chloroaniline and high boiling point solvents, m-cresol and isoquinoline
were cleared by ethanol reflux for 2 h at 80 °C. Yield: 78.4%
2.2.10. N,N′-Bis(2,6-diisopropylphenyl)-1,7-di-[4-sulfuric acid)phenoxy]
perylene-3,4,9,10-tetracarboxydiimide (4b)
N,N′-Bis(2,6-diisopropylphenyl-1,7-diphenoxy-perylene-3,4,9,10-
tetracarboxydiimide (25.06 g, 0.028 mol)was added to 500 mL of con-
centrated sulfuric acid and the flask was sealed. The mixture was stirred
at room temperature for 20 h 1000 mL of distilled water was added
dropwisely to form a precipitate, then filtered under low pressure. The
solid product was washed several times with DCM. Red product was
dried in a vacuum oven at 80 °C overnight. Yield: 75.0%; 1H NMR
(DMSO‑d6, ppm): 9.50 (d, 2H), 8.68 (d, 2H), 8.21 (s, 2H), 7.69 (d, 4H),
2.2.6. N,N′-Bis[4-(sulfuric acid)phenyl]-1,7-(disulfuric acid)perylene-
3,4,9,10-tetra carboxydiimide(3b)
A total of 27.40 g (0.039 mol) of N,N′-bis-[4-(sulfuric acid)phenyl]-
3,4,9,10-perylenebis(dicarboximide) with 160 ml of oleum (20% SO3)
were refluxed at 145 °C overnight. The hot solution was cooled at room
temperature and dropwised into 200 ml of DMF. Then, the mixture
solution was poured into 3000 ml of acetone, and the precipitate of 3b
was filtered out and dried at 40 °C under vacuum. In order to remove
the remaining sulfuric acid, the product was dissolved in 2000 ml of
distilled water. Yield: 70.3%; 1H NMR (DMSO‑d6, ppm): 8.81 (d, 4H),
8.10 (d, 4H), 7.91 (s, 2H), 7.67 (d, 2H), 7.40 (d, 2H); 13C NMR
(DMSO‑d6, ppm): δ = 31.24, 34.82, 36.27, 40.15, 118.34, 119.36,
122.25, 126.85, 131.67, 132.13, 133.77, 134.56, 138.95, 148.15,
149.01, 162.80; MALDI–TOF MS: m/z 863.59 (100%, [M + 4H]+);
Elemental analysis: Calcd for C36H18N2O16S4: C, 50.11; H, 2.10; N,
3.25; S, 14.87%. Found: C, 51.87; H, 2.37; N, 3.18; S, 14.45.
7.45 (t, 2H), 7.33 (d, 4H), 7.24 (d, 4H), 2.70 (m, 4H), 1.05 (d, 24H); 13
C
NMR (DMSO‑d6, ppm): δ = 30.59, 39.93, 41.90, 49.01, 118.50, 118.81,
122.58, 124.84, 126.05, 128.39, 128.79, 129.32, 129.86, 131.00,
131.27, 133.10, 142.30, 145.02, 145.95, 154.66, 155.50, 162.84,
163.41; MALDI–TOF MS: m/z 1057.63 (100%, [M + 2H]+); Elemental
analysis: Calcd for C60H50N2O12S2: C, 68.30; H, 4.78; N, 2.65; S, 6.08%.
Found: C, 69.15; H, 4.81; N, 2.78; S, 6.15.
2.2.11. 1,6,7,12-Tetrachloroperylene-3,4,9,10-tetracarboxylic
dianhydride
Perylene-3,4,9,10-tetracarboxylic dianhydride (20 g, 0.051 mol),
iodine (0.241 g, 1.90 mol), and 250 mL of chlorosulfuric acid were
mixed and stirred for 2 h at room temperature. The reaction tempera-
ture was increased to 70 °C and the mixture was heated for 16 h. The
mixture was slowly transferred to a litre of ice-water and red precipitate
was obtained. The precipitate was collected by suction filtration and
was washed with distilled water several times until the aqueous layer
became neutral to yield crude product. The product was dried in a
vacuum oven at 80 °C and used in the next step without further pur-
ification.
2.2.7. 1,7-Dibromo-perylene-3,4,9,10-tetracarboxylic dianhydride
Perylene-3,4,9,10-tetracarboxylic dianhydride (20 g, 0.051 mol),
iodine(0.241 g, 1.90 mol), and 300 ml of 98% sulfuric acid were mixed
and stirred for 2 h at room temperature. The reaction temperature was
increased to 80 °C and bromine(4.25 mL, 87.72 mmol) was added
dropwisely. The mixture was heated for 16h then cooled to room
temperature while displacing excess Br2(g) by flowing N2(g) into the
reaction flask. The mixture was slowly transferred to a litre of ice-water
and red precipitate was obtained. The precipitate was collected by
suction filtration and was washed with distilled water several times
until the aqueous layer became neutral to wield crude product. The
product was dried in a vacuum oven at 80 °C.
2.2.12. N,N′-Bis(2,6-diisopropylphenyl)-1,6,7,12-tetrachloroperylene-
3,4,9,10-tetracarboxydiimide
1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxydiimide
(30 g,
0.056 mol) was suspended in 1000 mL of propionic acid in a 2000 mL
RBF at 70 °C for 1 h. 2,6-diisopropylaniline (70 mL, 0.392 mol) was
added to the mixture after increasing the reaction temperature to 140 °C
and heated overnight. The mixture was cooled to room temperature and
was slowly transferred to 2000 mL of methanol. Filtrate was collected
after suction filtration; washed thoroughly with methanol. Crude pro-
duct was obtained after evaporating the filtrate in rotatory evaporator.
The product was purified by column chromatography on silica gel using
DCM as the eluent. A band containing tribrominated diimide was se-
parated first, followed by dibrominated and monobrominated. Yield:
75.6%
2.2.8. N,N′-Bis(2,6-diisopropylphenyl)-1,7-dibromo-perylene-3,4,9,10-
tetracarboxydiimide
1,7-dibromoperylene-3,4,9,10-tetracarboxydiimide (30 g, 0.054 mol)
was suspended in 900 mL of propionic acid in a 2000 mL RBF at 70 °C for
1 h. 2,6-diisopropylaniline (71.25 mL, 0.378 mol) was added to the
mixture after increasing the reaction temperature to 140 °C and heated
overnight. The mixture was cooled to room temperature and was slowly
transferred to 2000 mL of methanol. Filtrate was collected after suction
filtration; washed thoroughly with methanol. Crude product was ob-
tained after evaporating the filtrate in rotatory evaporator. The product
was purified by column chromatography on silica gel using di-
chloromethane(DCM) as the eluent. A band containing tribrominated
diimide was separated first, followed by dibrominated and mono-
brominated. Yield: 60.8%
2.2.13. N,N′-Bis(2,6-diisopropylphenyl)-1,6,7,12-tetraphenoxy-perylene-
3,4,9,10-tetracarboxydiimide
N,N′-Bis(2,6-diisopropylphenyl)-1,6,7,12-tetrachloroperylene-
3,4,9,10-tetracarboxydiimide (35.64 g, 0.042 mol)was suspended in
1000 mL of NMP with phenol(19.76 g, 0.21 mol). The mixture was
384