Solid-State Emitters
CDCl ): d=7.22 (d, 2H), 7.14–7.09 (m, 9H), 7.05–7.00 (m, 6H),
RT overnight (12 h). The reaction mixture was poured into H O
2
3
1
3
6
.89 ppm (d, 2H); C NMR (75 MHz, CDCl ): d=143.99, 143.37,
(200 mL) and extracted with CH
were combined and washed with H
tion, and brine then dried over anhydrous MgSO
2
Cl
2
(3ꢂ50 mL). The organic phases
O, 1m sodium thiosulfate solu-
. The crude prod-
3
1
42.27, 140.32, 133.66, 131.95, 131.52, 128.45, 127.35, 121.11 ppm;
2
+
HRMS (MALDI-TOF): m/z calcd for C H Br: 412.0670 [M+2H ];
4
26
19
found: 412.06810.
uct was purified by column chromatography on silica gel using n-
hexane as eluent to give 10 in 25.1% yield (1.21 g) as white solid.
4
-(1,2,2-triphenylvinyl)phenylboronic acid (5): n-Butyllithium
1
H NMR (300 MHz, CDCl ): d=8.14 (d, 2H), 8.11 (d, 2H), 7.25 ppm
3
(
2.5m in hexanes, 5.8 mL) was added to a solution of 4 (4 g,
13
(
t, 2H); C NMR (75 MHz, CDCl ): d=139.25, 135.33, 134.31, 129.12,
3
9
.7 mmol) in dry THF (50 mL) under nitrogen at À788C. After stir-
1
00.39 ppm; HRMS (MALDI-TOF): m/z calcd for C H I : 379.8559
10 6 2
ring at À788C for 3 h, trimethylborate (17.5 mmol, 2.0 mL) was
added to the reaction mixture. The mixture was warmed to RT and
the reaction was terminated by adding 2m HCl (10 mL). After stir-
+
[M ]; found: 377.9555.
BTPEAr compounds: The BTPEAr luminogens were synthesized by
a similar procedure as outlined here to give 67–96% yields. Briefly,
a mixture of 5 (2.0 mmol), dihaloarene (8, 10–12) (1.0 mmol),
ring for 12 h, the mixture was poured into H O and extracted with
CH Cl . The organic layer was washed with H O and dried over
2
2
2
2
MgSO . After filtration and solvent evaporation, the crude product
was purified by column chromatography on silica gel using n-
[Pd(PPh
toluene/H
3
)
4
] (0.05 mmol), and potassium carbonate (0.02 mmol) in
O (3:1 v/v, 100 mL) was heated to reflux for 24 h under
4
2
hexane/ethyl acetate (3:1) as eluent to give 5 in 74.9% yield
nitrogen. After filtration and solvent evaporation, the crude prod-
uct was purified by column chromatography on silica-gel using n-
1
(
2.74 g) as white solid. H NMR (300 MHz, CDCl ): d=7.88 (d, 2H),
3
13
7
1
1
.14–7.04 ppm (m, 19H); C NMR (75 MHz, CDCl ): d=148.95,
hexane/CH Cl (5:1) as eluent.
2 2
3
44.12, 142.43, 141.41, 135.62, 133.52, 132.00, 131.59, 128.41,
1
,4-Dimethyl-2,5-bis[4-(1,2,2-triphenylvinyl)phenyl]benzene
27.36 ppm; HRMS (MALDI-TOF): m/z calcd for C H BO : 376.1635
1
26
21
2
(BTPEPM): White solid; yield 66.8% (0.51 g); H NMR (300 MHz,
+
[M ]; found: 376.092.
13
CDCl ): d=7.26–7.04 (m, 20H), 2.20 ppm (s, 6H); C NMR (75 MHz,
3
1
,4-bis(hexyloxy)benzene (7): KOH (2.3 g, 40.9 mmol) and KI
CDCl ): d=144.43, 142.78, 141.76, 141.47, 141.12, 140.36, 133.20,
3
(
2
0.9 g, 5.5 mmol) were added to a mixture of hydroquinone (6, 3 g,
7.3 mmol) and 1-bromohexane (8.8 mL, 62.7 mmol) in acetone/
132.28, 132.08, 131.64, 129.15, 128.31, 127.10, 20.53 ppm: HRMS
(MALDI-TOF): m/z calcd for C60H46: 766.3600 [M ]; found: 766.4899;
+
DMSO mixture (9/1 v/v, 100 mL) and the resulting reaction mixture
was heated at reflux for 12 h. The acetone was subsequently
elemental analysis calcd (%) for C60
C 94.00, H 6.00.
H46: C 93.96; H 6.04; found:
evaporated at reduced pressure. After addition of H O, the residue
2
1
,2-Bis(hexyloxy)-2,5-bis[4-(1,2,2-triphenylvinyl)phenyl] benzene
was extracted with CHCl three times. The organic layer was further
1
3
(BTPEPOH): White solid; yield 96.5% (0.91 g); H NMR (300 MHz,
washed three times each with H O and brine, and was then dried
2
CDCl ): d=7.34 (d, 4H), 7.13–7.03 (m, 34H), 6.90 (s, 2H), 3.83 (t,
3
over anhydrous MgSO . After filtration and solvent evaporation,
4
4
H), 1.65–1.60 (m, 4H), 1.35–1.24 (m, 12H), 0.88 ppm (t, 6H);
the pale yellow crude product was purified by column chromatog-
13
C NMR (75 MHz, CDCl ): d=151.10, 144.54, 142.86, 141.55, 136.99,
3
raphy on silica gel using n-hexane as eluent to give 7 in 41.4%
1
3
32.15, 132.07, 131.56, 131.13, 129.39, 128.30, 127.08, 116.98, 70.35,
2.17, 30.03, 26.40, 23.27, 14.75 ppm; HRMS (MALDI-TOF): m/z
1
yield (3.14 g) as white solid. H NMR (300 MHz, CDCl ): d=6.81 (d,
3
4
H), 3.90 (t, 4H), 1.77–1.70 (m, 4H), 1.47–1.39 (m, 4H), 1.35–1.30
+
calcd for C H O : 938.5063 [M ]; found: 938.4984; elemental anal-
ysis calcd (%) for C H O : C 89.51, H 7.08, O 3.41; found: C 89.51,
H 6.96, O 3.53.
13
70 66
2
(
m, 8H), 0.90 ppm (t, 6H); C NMR (75 MHz, CDCl ): d=153.87,
3
70
66
2
1
16.06, 69.34, 32.30, 30.05, 26.43, 23.30, 14.73 ppm; HRMS (MALDI-
+
TOF): m/z calcd for C H O : 278.2246 [M ]; found: 278.9822.
1
8
30
2
1
,5-Bis[4-(1,2,2-triphenylvinyl)phenyl]naphthalene
(BTPENp):
1
,4-bis(hexyloxy)-2,5-diiodobenzene (8): Compound 7 (2 g,
1
White solid; yield 76.1% (0.60 g); H NMR (300 MHz, CDCl ): d=
3
7
.2 mmol), I (2.2 g, 8.6 mmol), and KIO (1.8 g, 8.6 mmol) in a solu-
2
3
7
3
1
1
7
.78 (d, 2H), 7.42–7.39 (m, 4H), 7.21 (d, 4H), 7.17–7.08 ppm (m,
4H); C NMR (75 MHz, CDCl ): d=144.37, 143.38, 141.98, 141.42,
40.97, 139.66, 132.62, 132.08, 131.84, 130.11, 128.39, 127.20,
26.28, 125.92 ppm; HRMS (MALDI-TOF): m/z calcd for C H :
tion of acetic acid/water/sulfuric acid (90:7:3 v/v/v, 50 mL) was
gently stirred and heated at 808C for 24 h. After cooling to RT, the
acetic acid was evaporated under reduced pressure. The crude io-
dinated product was washed consecutively with 1m sodium thio-
sulfate solution (100 mL), 1m sodium bicarbonate (20 mL), and
13
3
6
2
44
+
88.3443 [M ]; found: 788.2293; elemental analysis calcd (%) for
C H : C 94.38, H 5.62; found: C 94.52, H 5.48.
62
44
water (200 mL). The residue was extracted three times with CH Cl2
2
and then dried over anhydrous MgSO . After filtration and solvent
evaporation, the crude product was purified by column chroma-
9,10-Bis[4-(1,2,2-triphenylvinyl)phenyl]anthracene
(BTPEAn):
White solid; yield 71.0% (0.60 g); H NMR (300 MHz, CDCl ): d=
7.62 (d, 4H), 7.35 (d, 4H), 7.24–7.15 (m, 38H); C NMR (75 MHz,
CDCl ): d=143.77, 132.07, 131.92, 131.35, 130.41, 128.49, 128.28,
127.65, 127.24, 125.53. HRMS (MALDI-TOF): m/z calcd for C66H :
46
4
1
3
13
tography on silica gel using n-hexane as eluent to give 8 in 20.4%
1
yield (0.78 g) as white solid. H NMR (300 MHz, CDCl ): d=7.17 (s,
3
3
2
H), 3.93 (t, 4H), 1.83–1.76 (m, 4H), 1.52–1.48 (m, 4H), 1.36–1.34
13
+
(
m, 8H), 0.91 ppm (t, 6H); C NMR (75 MHz, CDCl ): d=153.56,
838.3600 [M ]; found: 838.4308; elemental analysis calcd (%) for
C H46: C 94.47, H 5.53; found: C 94.35, H 5.65.
66
3
1
23.49, 87.00, 71.06, 32.16, 29.80, 26.40, 23.28, 14.73 ppm; HRMS
+
(
MALDI-TOF): m/z calcd for C H I O : 530.0179 [M ]; found:
18 28 2 2
5
30.1025.
1
,5-diiodonaphthalene (10): Sodium nitrite (1.8 g, 26.6 mmol) in
water (25 mL) was slowly added to an ice-cold mixture of 1,5-dia-
minonaphthalene (9, 2 g, 12.6 mmol) in concentrated HCl (10 mL)
Acknowledgements
and H O (10 mL) while maintaining the temperature below 58C.
The reaction mixture was stirred for 10 min at 08C, after which KI
2
This study was supported by RPC and SRFI grants of HKUST
(
RPC11SC09, RPC10SC13, and SRFI11SC03PG), the Research
(
5.3 g, 31.6 mmol) in H O (40 mL) was added dropwise. Afterward,
2
Grants Council of Hong Kong (604711, 603509, HKUST2/CRF/10,
and N HKUST620/11), the National Natural Science Foundation
the mixture was heated at reflux for 30 min, cooled and stirred at
ChemPlusChem 2012, 00, 1 – 11
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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