Full Paper
2b: Isolated in 85 % yield as an orange solid. M.p. 240 °C. Td
=
serve as a new approach to the tuning of the solid-state lumi-
nescent properties of such fluorophores.
279 °C. TLC: Rf = 0.26 (hexane/CH2Cl2, 1:1). 1H NMR (CDCl3,
300 MHz): δ = 6.96 (d, J = 7.5 Hz, 4 H), 7.04 (t, J = 7.2 Hz, 4 H), 7.11
(d, J = 7.5 Hz, 8 H), 7.26–7.32 (m, 14 H), 7.45 (s, 2 H) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 123.0, 123.5, 126.9, 129.0, 129.3, 129.4, 129.6,
Experimental Section
134.6, 138.8, 141.2, 147.2, 190.1 ppm. IR (KBr): ν = 3441, 3059, 1674,
˜
1589, 1493, 1479, 1285, 1248, 1157, 976, 866, 746, 691 cm–1. HRMS
(FAB): calcd. for C44H32O2N2S2 684.1905 [M]+; found 684.1896.
General: Melting points were determined by using a Seiko TG/
1
DTA6200 Instrument. H NMR spectra were recorded with a Bruker
Avance II 300 (300 MHz) spectrometer. The chemical shifts of the
1H NMR spectra are expressed in parts per million downfield relative
to internal tetramethylsilane (δ = 0 ppm) or chloroform (δ =
7.26 ppm). Splitting patterns are indicated as follows: s, singlet; d,
doublet; t, triplet; q, quartet. 13C NMR spectra were recorded with
a Varian Mercury 400 (100 MHz) spectrometer with tetramethyl-
silane (δ = 0 ppm) or [D]chloroform (δ = 77.0 ppm) as internal
standard. 19F NMR spectra were recorded with a Bruker Avance II
300 (282 MHz) spectrometer with C6F6 as internal standard (δ =
–163.7 ppm). Chemical shifts are given in parts per million down-
field relative to the internal standards. IR spectra were recorded
with a Shimadzu FTIR-8400 spectrometer. HRMS (FAB) analyses were
performed with a JEOL JMS-700 spectrometer. TLC analyses were
performed on Merck Kieselgel 60 F254. Silica gel column chromatog-
raphy was carried out on Merck Kieselgel 60 (230–400 mesh). Rea-
gent-grade dichloromethane was passed through two packed col-
umns of neutral alumina and copper oxide under nitrogen before
use.
2c: Isolated in 93 % yield as an orange solid. M.p. 279 °C (decomp.).
TLC: Rf = 0.31 (hexane/EtOAc, 5:1). 1H NMR (CDCl3, 300 MHz): δ =
3.77 (s, 6 H), 6.83 (dd, J = 9.0, 9.0 Hz, 8 H), 7.03 (t, J = 7.2 Hz, 4 H),
7.10 (d, J = 7.5 Hz, 8 H), 7.28 (dd, J = 7.5, 7.2 Hz, 8 H), 7.44 (s, 2 H)
ppm. 13C NMR (CDCl3, 100 MHz): δ = 55.3, 114.7, 117.5, 122.9, 123.5,
129.3, 129.7, 136.2, 138.9, 141.2, 147.2, 160.7, 191.1 ppm. IR (KBr):
ν = 3443, 3036, 1672, 1591, 1493, 1385, 1250, 1173, 1030, 870,
˜
827 cm–1. HRMS (FAB): calcd. for C46H36O4N2S2 744.2116 [M]+; found
744.2122.
2d: Isolated in 92 % yield as an orange solid. M.p. 271 °C (decomp.).
1
TLC: Rf = 0.24 (hexane/CH2Cl2, 3:2). H NMR (CDCl3, 300 MHz): δ =
2.30 (s, 6 H), 6.83 (d, J = 7.8 Hz, 4 H), 7.01–7.11 (m, 16 H), 7.28 (dd,
J = 7.5, 7.2 Hz, 8 H), 7.44 (s, 2 H) ppm. 13C NMR (CDCl3, 100 MHz):
δ = 21.3, 122.9, 123.4, 123.5, 129.3, 129.7, 129.8, 134.5, 138.9, 139.7,
141.2, 147.2, 190.6 ppm. IR (KBr): ν = 3443, 3036, 1674, 1587, 1485,
˜
1385, 1277, 1250, 1165, 910, 868, 808, 748, 694 cm–1. HRMS (FAB):
calcd. for C46H36O2N2S2 712.2218 [M]+; found 712.2220.
Measurement of Photoluminescence: The spectroscopic-grade
toluene for photoluminescence measurements was purchased from
Kanto Chemical Co., Inc. and degassed with argon before use. Pho-
toluminescence spectra and absolute quantum yields were re-
corded with a Hamamatsu Photonics C9920-02 Absolute PL Quan-
tum Yield Measurement System.
2e: Isolated in 92 % yield as an orange solid. M.p. 316 °C (decomp.).
TLC: Rf = 0.19 (hexane/CH2Cl2, 2:1). H NMR (CDCl3, 300 MHz): δ =
1.27 (s, 18 H), 6.88 (d, J = 8.4 Hz, 4 H), 7.04 (t, J = 7.5 Hz, 4 H), 7.11
(d, J = 8.7 Hz, 8 H), 7.26–7.32 (m, 12 H), 7.45 (s, 2 H) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 31.2, 34.7, 122.9, 123.4, 123.5, 126.2, 129.3,
1
129.7, 134.2, 139.0, 141.2, 147.2, 152.7, 190.7 ppm. IR (KBr): ν = 3431,
˜
Typical Procedure for the Hydrolysis of 1: A 100 mL two-necked
flask was charged with 1a (1.98 g, 3.74 mmol), THF (20 mL), EtOH
2963, 1686, 1668, 1589, 1485, 1391, 1275, 1250, 1167, 872, 826, 750,
694 cm–1. HRMS (FAB): calcd. for C52H48O2N2S2 796.3157 [M]+;
found, 796.3149.
(15 mL), and 8
for 16 h. The organic solvent was removed by rotary evaporation
under reduced pressure. The residue was neutralized with 1 HCl
M aq. NaOH (15 mL). The mixture was stirred at 80 °C
2f: Isolated in 80 % yield as an orange solid. M.p. 273 °C (decomp.).
M
1
TLC: Rf = 0.47 (hexane/CH2Cl2, 3:2). H NMR (CDCl3, 300 MHz): δ =
until the resulting solution reached a pH of 1. The precipitates were
collected by filtration and dried at 80 °C for 16 h to give 2,5-bis(di-
phenylamino)terephthalic acid (1.86 g, 3.72 mmol, 99 %) as a red
solid.
7.04–7.12 (m, 16 H), 7.30 (dd, J = 8.4, 7.5 Hz, 8 H), 7.43 (s, 2 H), 7.52
(d, J = 8.1 Hz, 4 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 123.3,
123.6, 123.7 (q, J = 270.7 Hz), 125.8 (q, J = 3.8 Hz), 129.4, 129.5,
131.4 (q, J = 32.0 Hz), 131.5, 134.8, 138.3, 141.3, 147.1, 188.8 ppm.
19F NMR (CDCl3, 282 MHz): δ = –65.0 ppm. IR (KBr): ν = 3447, 3065,
Typical Procedure for the Synthesis of 2: A 30 mL two-necked
flask was charged with 2,5-bis(diphenylamino)terephthalic acid
(0.25 g, 0.50 mmol), 4-(dimethylamino)pyridine (DMAP; 12 mg,
0.10 mmol), dicyclohexylcarbodiimide (DCC; 0.23 g, 1.10 mmol), and
CH2Cl2 (2 mL). PhSH (110 μL, 1.10 mmol) was slowly added to the
flask at 0 °C. The reaction mixture was stirred at 35 °C for 16 h. The
solution was diluted with CHCl3 (30 mL), and the resulting solution
was washed with a satd. aq. NaHCO3 solution (3 × 30 mL). The
aqueous layer was extracted with CHCl3 (3 × 30 mL). The combined
organic layers were dried with anhydrous MgSO4, filtered, and con-
centrated by solvent evaporation. The crude product was purified
by silica gel column chromatography (eluent: hexane/CH2Cl2, 2:1)
to give 2b (0.29 g, 0.42 mmol, 85 %) as an orange solid.
˜
1690, 1665, 1589, 1493, 1391, 1325, 1250, 1165, 1130, 1063, 874,
837, 752, 696 cm–1. HRMS (FAB): calcd. for C46H30O2N2F6S2 820.1653
[M]+; found 820.1642.
2g: Isolated in 93 % yield as an orange solid. M.p. 227 °C (decomp.).
1
TLC: Rf = 0.24 (hexane/CH2Cl2, 3:2). H NMR (CDCl3, 300 MHz): δ =
1.96 (s, 6 H), 6.93 (d, J = 7.8 Hz, 2 H), 7.00–7.12 (m, 14 H), 7.16–7.30
(m, 12 H), 7.51 (s, 2 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 20.4,
123.0, 123.2, 126.35, 126.43, 129.3, 130.1, 130.6, 135.9, 139.3, 141.4,
142.4, 147.2, 189.4 ppm. IR (KBr): ν = 3.937, 3927, 1680, 1587, 1485,
˜
1385, 1275, 1246, 870, 752, 696 cm–1. HRMS (FAB): calcd. for
C46H36O2N2S2 712.2218 [M]+; found 712.2220.
2a: Isolated in 85 % yield as a yellow solid. M.p. 240 °C (decomp.).
TLC: Rf = 0.60 (hexane/CH2Cl2, 2:3). H NMR (CDCl3, 300 MHz): δ =
2h: Isolated in 84 % yield as an orange solid. M.p. 269 °C (decomp.).
TLC: Rf = 0.58 (hexane/CH2Cl2, 2:3). H NMR (CDCl3, 300 MHz): δ =
1
1
3.86 (s, 4 H), 6.96–7.03 (m, 16 H), 7.19–7.25 (m, 14 H), 7.37 (s, 2 H)
ppm. 13C NMR (CDCl3, 100 MHz): δ = 33.9, 122.8, 123.3, 127.2, 128.5,
129.0, 129.2, 129.8, 136.4, 139.0, 141.2, 147.1, 191.3 ppm. IR (KBr):
6.95 (dd, J = 8.7, 1.8 Hz, 2 H), 7.08 (t, J = 7.5 Hz, 4 H), 7.14 (d, J =
8.7 Hz, 8 H), 7.32 (dd, J = 8.7, 7.5 Hz, 8 H), 7.45–7.49 (m, 4 H), 7.51–
7.53 (m, 4 H), 7.70–7.80 (m, 6 H) ppm. 13C NMR (CDCl3, 100 MHz):
δ = 123.0, 123.6, 124.2, 126.4, 127.1, 127.7, 127.9, 128.5, 129.4, 129.6,
130.9, 133.3, 133.4, 134.7, 138.8, 141.2, 127.2, 190.3 ppm. IR (KBr):
ν = 3443, 3030, 1663, 1643, 1587, 1493, 1485, 1451, 1391, 1387,
˜
1271, 1250, 876, 754, 696 cm–1. HRMS (FAB): calcd. for C46H36O2N2S2
712.2218 [M]+; found 712.2217.
ν = 3447, 3053, 1680, 1587, 1491, 1385, 1256, 874, 814, 752,
˜
Eur. J. Org. Chem. 0000, 0–0
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim