662
S. Kuster, T. Geiger / Dyes and Pigments 95 (2012) 657e670
chromatography (chloroform) yielded BSQ 1 (1.1 g, 0.85 mmol,
(2 mL, 1 N) was added. The reaction was completed by refluxing for
an additional day. Subsequently, the solvent was removed under
reduced pressure. The concentrate was diluted with ethanol
(10 mL) and poured into water (250 mL). The suspension was
stirred for 30 min and the precipitate was filtered. The residue was
digested with diethyl ether several times. Subsequent purification
by column chromatography (chloroform) yielded BSQ 3 (0.48 g,
0.33 mmol, 29%). d.p. 287 ꢁC. 1H NMR (CDCl3, 400 MHz, ppm):
65%). d.p. 300 ꢁC. 1H NMR (CDCl3, 400 MHz, ppm):
d 8.18 (d,
3J ¼ 8.5 Hz, 2H, H-9*), 7.86 (d, 3J ¼ 8.1 Hz, 2H, H-6*), 8.84 (d,
3J ¼ 8.8 Hz, 2H, H-5*), 7.66 (s, 4H, H-2x), 7.6e7.5 (m, 6H, H-8*, H-4yy,
3
3
H-6yy), 7.38 (dd, J ¼ 8.1 Hz, 7.5 Hz, 2H, H-7*), 7.27 (d, J ¼ 8.8 Hz,
2H, H-4*), 7.03 (d, 3J ¼ 8.2 Hz, 2H, H-7yy), 6.04 (s, 2H, H-100), 5.95 (s,
2H, H-10), 4.10 (br, 4H, H-1y), 3.52 (br, 6H, H-1zz), 2.06 (s, 12H, H-
1**), 2.0e1.8 (m, 16H, H-1z, H-2y), 1.5e1.2 (m, 20H, H-3y, H-4y, H-5y,
H-6y, H-7y), 0.84 (t, 3J ¼ 6.8 Hz, 6H, H-8y). For numeration see
Supplemental Information. 13C NMR (CDCl3, 100 MHz, ppm):
4
3
d
8.21 (dd, 3J ¼ 8.4 Hz, J ¼ 1.0 Hz, 2H, H-9*), 7.90 (dd, J ¼ 8.0 Hz,
4J ¼ 1.2 Hz, 2H, H-6*), 7.88 (d, 3J ¼ 9.0 Hz, 2H, H-5*), 7.66 (d,
4J ¼ 1.5 Hz, 2H, H-4yy), 7.58 (ddd, 3J ¼ 8.4 Hz, 7.0 Hz, 4J ¼ 1.2 Hz, 2H,
H-8*), 7.51 (dd, 3J ¼ 8.2 Hz, 4J ¼ 1.5 Hz, 2H, H-6yy), 7.42 (ddd,
3J ¼ 8.0 Hz, 7.0 Hz, 4J ¼ 1.0 Hz, 2H, H-7*), 7.31 (d, 3J ¼ 9.0 Hz, 2H, H-
4*), 7.05 (d, 3J ¼ 8.2 Hz, 2H, H-7yy), 6.99 (s, 2H, H-3x), 6.1e5.8 (m,
4H, H-10, H-100), 4.2e4.0 (m, 4H, H-1y), 4.0e3.7 (m, 4H, H-1xx),
3.7e3.5 (br, 6H, H-1zz), 2.07 (s, 12H, H-1**), 2.0e1.7 (m, 16H, H-1z,
H-2y), 1.7e1.5 (m, 4H, H-2xx), 1.5e1.1 (m, 36H, H-3y, H-4y, H-5y, H-
6y, H-7y, H-3xx, H-4xx, H-5xx, H-1#), 0.86 (m, 18H, H-8y, H-6xx, H-
2#). For numeration see Supplemental Information. 13C NMR
d
182.27, 179.74, 177.49, 172.13, 169.24, 142.55, 142.45, 139.26,
135.93, 134.50, 131.15, 129.53, 128.41, 127.18, 127.14, 126.43, 124.29,
122.40, 120.59, 110.05, 109.04, 86.84, 86.48, 51.22, 48.79, 43.78,
31.51, 29.12, 28.94, 27.25, 27.14, 26.83, 26.50, 22.39, 13.90.
MS(MALDI): 1220 (100) [M þ H]þ, 1219 (82) [M]þ, 1205 (24)
[M þ HeCH3]þ, 1190 (10) [M þ He2xCH3]þ, 912 (16) [C62H62N3O4]þ,
805 (11) [C56H59N3O2]þ, 790 (6) [C55H56N3O2]þ, 609.8 (4)
[M
þ
H]þþ 609.3 (3) [M]þþ 414 (12) [C28H32NO2]þ. HR-
, ,
MS(MALDI): calculated for C84H90N4O4 [M]þ: 1218.6957. Found:
1218.6980. Elemental analysis: calculated for C84H90N4O4: C, 82.72;
H, 7.44; N, 4.59; O, 5.25. Found: C, 82.45; H, 7.50; N, 4.65; O, 5.45.
(CDCl3, 100 MHz, ppm):
d 182.43, 178.68, 177.47, 172.13, 170.04,
166.59, 150.35, 141.45 139.46, 134.63, 134.07, 131.28, 130.14, 129.67,
129.65, 128.86, 128.60, 127.31, 124.39, 123.86, 122.59, 120.27, 115.54,
110.18, 108.47, 86.88, 86.54, 71.61, 51.32, 49.06, 43.95, 39.59, 31.72,
31.69, 30.40, 29.30, 29.11, 28.97, 27.40, 27.21, 27.01, 26.66, 23.88,
22.95, 22.55, 14.03, 11.01. MS(MALDI): 1498 (3) [M þ Na]þ, 1476
(100) [M þ H]þ, 1475 (55) [M]þ, 1461 (11) [M þ HeCH3]þ, 1446 (2)
[M ꢀ C2H5]þ, 1169 (6) [C78H94N3O6]þ, 1077 (12) [C73H94N3O4]þ,
1062 (7) [C72H91N3O4]þ, 738 (1) [M þ H]þþ. HR-MS(MALDI):
2.2.7. 2,20-(5,50-(9,9-Bis(2-ethylhexyl)-9H-fluorene-2,7-diyl)
bis(1,3,3-trimethyl-indoline-5-yl-2-ylidene))bis(methan-1-yl-1-
ylidene)bis(4-((1,1-dimethyl-3-octyl-1H-benzo[e]indolium-2-yl)
methylene)-3-oxocyclobut-1-enolate) (BSQ 2)
Fluorene bridge 30 (1.00 g, 0.928 mmol, Supplemental
Information), half dye 34 (1.02 g, 2.32 mmol, Supplemental
Information) were dissolved in toluene (10 mL), 1-butanol
(10 mL) and 1-methyl-2-pyrrolidinone (10 mL) and heated to
reflux for 2 d. Afterwards, the solvent was removed under vacuum
and the concentrate was dissolved in ethanol (25 mL). This solution
was poured into ice-water (1 L) under vigorously stirring. After 1 h,
the precipitate was filtered off and dissolved in chloroform
(200 mL). The organic phase was extracted with saturated citric
acid (2 ꢂ 150 mL), water (4 ꢂ 150 mL) and brine (150 mL). After
evaporating the solvent under reduced pressure, the remnant was
suspended in diethyl ether (2 ꢂ 50 mL) to dissolve the intermedi-
ates and side products. After filtration and drying in a vacuum oven
BSQ 2 (1.2 g, 0.76 mmol, 82%) was isolated as a dark blue amor-
calculated for C100H123O6N4 [M
1475.9468.
þ
H]þ: 1475.9437. Found:
2.2.9. 2,20-(5,50-(Perfluoro-1,4-phenylene)bis(1,3,3-trimethyl-indoline-
5-yl-2-ylidene))bis(methan-1-yl-1-ylidene)bis(4-((1,1-dimethyl-3-
octyl-1H-benzo[e]indolium-2-yl)methylene)-3-oxocyclobut-1-enolate)
(BSQ 4)
In a DeaneStark apparatus half dye 34 (474 mg, 1.08 mmol,
Supplemental Information), tetrafluoro phenylene bridge 32
(300 mg, 0.433 mmol, Supplemental Information), toluene (5 mL),
1-butanol (5 mL) and 1-methyl-2-pyrrolidinone (5 mL) were
combined to generate BSQ04 within 7 d at 120 ꢁC. Due to a change
of the pH value to about 7.5, the reaction preceded very slowly
which was controlled by UVevis measurements. Therefore,
aqueous hydrochloric acid (2 mL, 1 N) was added and the reaction
mixture was heated for an additional 2 d. Then, the reaction
mixture was concentrated under reduced pressure and the
remnant was dissolved in ethanol (10 mL). Under vigorously stir-
ring, the solution was added drop wise to water (1 L). After 30 min,
the suspension was filtered and the residue was digested in diethyl
ether several times to yield BSQ 4 (0.39 g, 0.30 mmol, 69%). d.p.
phous powder. d.p. 283 ꢁC. 1H NMR (CDCl3, 400 MHz, ppm):
d 8.21
(d, 3J ¼ 8.4 Hz, 2H, H-9*), 7.91 (d, 3J ¼ 8.0 Hz, 2H, H-6*), 7.88 (d,
3J ¼ 9.2 Hz, 2H, H-5*), 7.78 (d, 3J ¼ 8.1 Hz, 2H, H-4x), 7.65e7.55 (m,
10H, H-8*, H-4yy, H-6yy, H-1x, H-3x), 7.43 (ddd, 3J ¼ 8.0 Hz, 7.0 Hz,
4J ¼ 0.8 Hz, 2H, H-7*), 7.31 (d, 3J ¼ 9.2 Hz, 2H, H-4*), 7.05 (d,
3J ¼ 8.5 Hz, 2H, H-7yy), 6.15e5.9 (m, 4H, H-10, H-100), 4.2e4.0 (m, 4H,
H-1y), 3.7e3.5 (br, 6H, H-1zz), 2.2e2.0 (m, 16H, H-1xx, H-1**),
2.0e1.7 (m, 16H, H-1z, H-2y), 1.5e1.2 (m, 24H, alkyl chain), 1.0e0.7
(m, 20H, alkyl chain), 0.65e0.5 (m, 10H, alkyl chain). MS(MALDI):
1532 (100) [M þ H]þ, 1517 (14) [M þ HeCH3]þ, 1225 (4)
[C85H99N3O4]þ, 1118 (2) [C79H95N3O2]þ, 766 (1) [M þ H]þþ. HR-
MS(MALDI): calculated for C107H127N4O4 [M þ H]þ: 1531.9852.
Found: 1531.9823.
283 ꢁC. 1H NMR (CDCl3, 400 MHz, ppm):
d
8.21 (d, 3J ¼ 8.5 Hz, 2H, H-
9*), 7.91 (d, 3J ¼ 8.3 Hz, 2H, H-6*), 7.89 (d, 3J ¼ 8.6 Hz, 2H, H-5*), 7.59
(dd, 3J ¼ 8.5 Hz, 7.0 Hz, 2H, H-8*), 7.5e7.4 (m, 6H, H-4yy, H-6yy, H-
3
3
7*), 7.32 (d, J ¼ 8.6 Hz, 2H, H-4*), 7.05 (d, J ¼ 8.4 Hz, 2H, H-7yy),
6.12 (br, 2H, H-100), 6.00 (br, 2H, H-10), 4.18 (m, 4H, H-1y), 3.56 (br,
6H, H-1zz), 2.07 (s, 12H, H-1**), 2.0e1.7 (m, 16H, H-1z, H-2y), 1.5e1.2
(m, 20H, H-3y, H-4y, H-5y, H-6y, H-7y), 0.87 (t, 3J ¼ 6.5 Hz, 6H, H-8y).
For numeration see Supplemental Information. 13C NMR (CDCl3,
2.2.8. 2,20-(5,50-(2,5-Bis(2-ethylhexyloxy)-1,4-phenylene)bis(1,3,3-
trimethyl-indoline-5-yl-2-ylidene))bis(methan-1-yl-1-ylidene)
bis(4-((1,1-dimethyl-3-octyl-1H-benzo[e]indolium-2-yl)
methylene)-3-oxocyclobut-1-enolate) (BSQ 3)
100 MHz, ppm): d 182.44, 178.68, 177.47, 173.36, 170.04, 168.89,
In a DeaneStark apparatus half dye 34 (1.25 g, 2.85 mmol,
Supplemental Information), alkoxyphenylene bridge 31 (1.00 g,
1.14 mmol, Supplemental Information), toluene (5 mL), 1-butanol
(5 mL) and 1-methyl-2-pyrrolidinone (5 mL) were mixed and
heated to reflux for 2 d. According to UVevis measurements the
reaction proceeded slowly and the pH changed from 6 to 7.5. In
order to acidify the reaction mixture, aqueous hydrochloric acid
145.49, 143.84, 142.86, 142.25, 139.23, 135.10, 131.51, 130.70, 130.02,
129.80, 129.70, 128.53, 127.44, 124.70,124.05, 122.66, 121.99, 110.28,
108.71, 87.32, 87.07, 51.64, 48.69, 44.18, 31.69, 30.43, 29.29, 29.10,
27.51, 27.22, 27.00, 26.56, 22.55, 14.03. 19F NMR (CDCl3, 376 MHz,
ppm):
d
ꢀ144.4 (s, 4F, F-2x). MS(MALDI): 1314 (2) [M þ Na]þ, 1292
(100) [M þ H]þ,1277 (16) [M þ HeCH3]þ,1262 (7) [M ꢀ C2H5]þ, 984
(5) [C62H58F4N3O4]þ, 877 (4) [C56H55F4N3O2]þ, 720 (8)