(20 mL) at ꢀ78 ꢁC and then the mixture was stirred at
purified through recrystallization (CH2Cl2–hexane) to yield 4
ꢁ
that temperature for
1
h. 2-Isopropoxy-4,4,5,5-tetrame-
(2.85 g, 83%). M.p. 398 C (DSC); nmax(film)/cmꢀ1 3011, 1511,
1
thyl[1,3,2]dioxaborolane (0.6 mL, 3.0 mmol) was added at
ꢀ78 ꢁC and then the mixture was warmed to room temperature
slowly over a period of 6 h. The mixture was quenched with water
and extracted twice with CH2Cl2. The combined organic phases
were dried (MgSO4) and concentrated in vacuo. The residue was
purified by recrystallization (CH2Cl2/pentane) to yield 2 (833 mg,
78%) as a white solid. M.p. 137–140 ꢁC; nmax(film)/cmꢀ1 2970,
1434, 1311, 1173, 860, 799 cmꢀ1; H NMR (CDCl3, 400 MHz)
d 7.32 (2H, s, Ar–H), 7.11 (8H, d, J 8.0, Ar–H), 7.08 (8H, d, J 8.0,
Ar–H), 6.97 (2H, s, Ar–H), 2.33 (12H, s, 4 ꢂ Ar–CH3); 13C NMR
(CDCl3, 100 MHz) d 154.4, 152.2, 141.1, 140.9, 136.5, 134.8,
129.0, 127.6, 125.7, 117.0, 113.7, 63.3, 21.1; MS (m/z, FAB+)
154.1 (100); HRMS Calcd for C44H3279Br2S2 782.0312, found
782.0325; HRMS Calcd for C44H3279Br81BrS2 784.0292,
found 784.0330; HRMS Calcd for C44H3281Br2S2 786.0271,
found 786.0272.
1
1593, 1490, 1352, 1142, 1075, 845, 732 cmꢀ1; H NMR (CDCl3,
400 MHz) d 8.00 (1H, s, Ar–H), 7.95 (1H, d, J 7.6, Ar–H), 7.89–
7.86 (2H, m, Ar–H), 7.62ꢀ7.60 (2H, m, Ar–H), 7.53ꢀ7.48 (3H,
m, Ar–H), 7.46–7.41 (3H, m, Ar–H), 7.39–7.34 (4H, m, Ar–H),
7.34–7.23 (2H, m, Ar–H), 7.13 (1H, d, J 8.4, Ar–H), 2.37 (3H s,
Ar–CH3), 1.39 (12H, s, 4 ꢂ CH3); 13C NMR (CDCl3, 100 MHz)
d 151.4, 150.7, 150.0, 144.5, 142.5, 142.1, 140.2, 139.3, 138.7,
135.6, 133.8, 131.7, 128.5, 128.2, 128.1, 127.7, 127.6, 127.3, 126.6,
126.5, 126.4, 125.8, 125.7, 120.2, 119.8, 119.1, 83.6, 64.9, 25.2,
21.3; MS (m/z, FAB+) 534.2 (100); HRMS Calcd for C38H35BO2
534.2730, found 534.2755.
Synthesis of DPAInT2
Pd(OAc)2 (56 mg, 0.25 mmol), HNPh2 (1.10 g, 6.5 mmol), Nat-
BuO (3.60 mg, 37.5 mmol), and 4 (1.96 g, 2.5 mmol) were placed
in a 250 mL two-neck flask equipped with a septum. The flask
was evacuated and back-filled with argon. Toluene (50 mL) and
tBu3P (0.05 M in toluene, 10 mL, 0.5 mmol) were added
sequentially via syringe at room temperature. After heating at
110 ꢁC for 48 h, the reaction mixture was cooled to room
temperature and quenched with water (80 mL). The mixture was
extracted with CH2Cl2 (3 ꢂ 80 mL). The combined organic
phases were dried (MgSO4) and concentrated in vacuo to yield
DPAInT2 (2.20 g, 91%), which was purified through recrystalli-
zation (CH2Cl2–hexane). M.p. 423 ꢁC (DSC); nmax(film)/cmꢀ1
Synthesis of green emitter DFBTA
Pd(PPh3)4 (115 mg, 0.1 mmol), 4,7-dibromobenzo[1,2,5]thiadi-
azole (293 mg, 1.0 mmol), and 2-(9-biphenyl-9-tolyl-
fluorene)pinacol boronate (1175 mg, 2.0 mmol) were placed into
a 250 mL two-neck flask equipped with a septum. The flask was
evacuated and back-filled with argon. Toluene (50 mL), K2CO3
(1.4 mL, 1.5 M, 2.1 mmol), and tBu3P (0.05 M in toluene, 2 mL,
0.1 mmol) were added to tꢁhe flask via syringe at room tempera-
ture. After heating at 110 C for 72 h, the reaction mixture was
cooled to room temperature, water (80 mL) was added, and the
mixture was extracted with CH2Cl2 (3 ꢂ 80 mL). The combined
organic phases were dried (MgSO4) and concentrated in vacuo to
yield DFBTA (568 mg, 60%) as a yellow solid, which was purified
through column chromatography (CHCl3–toluene–hexane, 1 : 3 :
3). M.p. > 400 ꢁC (DSC); nmax(film)/cmꢀ1 3065, 3032, 1600, 1487,
1449, 1016, 731 cmꢀ1; 1H NMR (CDCl3, 400 MHz) d 8.06 (2H, d,
J 8.8, Ar–H), 7.97 (2H, s, Ar–H), 7.92 (2H, d, J 8.0, Ar–H), 7.83
(2H, d, J 7.2, Ar–H), 7.69 (2H, s, Ar–H), 7.52 (4 H, d, J 7.2, Ar–
H), 7.84–7.27 (20H, m, Ar–H), 7.21 (4H, d, J 8.4, Ar–H), 7.06
(4H, d, J 8.4, Ar–H), 2.29 (6H, s, 2 ꢂ Ar–CH3); 13C NMR
(CDCl3, 100 MHz) d 153.9, 151.5, 144.8, 142.5, 140.5, 140.2,
139.5, 139.2, 136.6, 136.1, 133.1, 128.8, 128.5, 128.0, 127.8, 127.7,
127.4, 126.9, 126.8, 126.1, 120.3, 120.0, 65.1, 21.0; MS (m/z,
FAB+) 949.5 (60), 391.3 (80), 307.0 (100); HRMS Calcd for
C70H48N2S 948.3538, found 948.3953; Anal. Calcd for
C70H48N2S C, 88.57, H 5.10, N, 2.95, found C, 88.58, H, 4.46,
N, 2.84.
1
1593, 1475, 1398, 1239, 758, 697 cmꢀ1; H NMR (CD2Cl2, 400
MHz) d 7.20–7.16 (12H, m, Ar–H), 7.07–7.05 (10H, m, Ar–H),
7.02 (8H, d, J 8.4,), 6.97 (10H, d, J 8.4, Ar–H), 2.23 (12H, s, 4 ꢂ
Ar–CH3); 13C NMR (CD2Cl2, 400 MHz) d 125.4, 124.9, 124.6,
124.4, 124.1, 123.1, 119.1, 16.4; MS (m/z, FAB+) 960 (5); HRMS
Calcd for C68H52N2S2 960.3572, found 960.3552; Anal. Calcd for
C68H52N2S2 C, 84.96; H, 5.45; N, 2.91; found C, 84.75; H, 5.46;
N, 2.82.
Synthesis of dibromide 6
A solution of Br2 (1.41 g, 8.8 mmol, 2.2 eq.) in CHCl3 (15 mL)
was added dropwise to a stirred solution of 5 (2.46 g, 4 mmol, 1
eq.) and FeCl3 (32 mg, 0.2 mmol, 0.05 eq.) in CHCl3 (15 mL) at
0 ꢁC. After stirring for 5 h, the solution was quenched with 2 M
K2CO3 (20 mL). The mixture was extracted twice with CHCl3.
The combined organic phases were washed with brine, dried
(MgSO4), and then concentrated through rotary evaporation.
After washing with hexane, the product was obtained as a white
solid (2.74 g, 95%). M.p. >400 ꢁC; nmax(film)/cmꢀ1 n 3054, 2987,
1
1422, 1265, 896, 742, 705 cmꢀ1; H NMR (CDCl3, 400 MHz)
d 7.67(2H, s, Ar–H), 7.50–7.47 (4H, m, Ar–H) 7.42 (2H, dd, J 1.6
and 8.4, Ar–H), 7.11 (8H, d, J 8.4, Ar–H), 7.07 (8H, d, J 8.4, Ar–
H), 3.33 (12H, s, 4 ꢂ Ar–CH3); 13C NMR (CDCl3, 100 MHz)
d 153.6, 151.1, 142.1, 139.2, 138.7, 136.4, 130.4, 129.1, 129.0,
127.9, 121.4, 121.2, 117.6, 64.6, 21.1; MS (m/z, FAB+) 774 (3.3);
HRMS (m/z, FAB+) Calcd for C48H3681Br2 774.1143, found
774.1177; Calcd for C48H3681Br79Br 772.1163, found 772.1196;
Calcd for C48H3679Br2 770.1184, found 770.1157.
Synthesis of dibromide 4
Compound 3 (2.75 g, 4.37 mmol) was dissolved in CHCl3
(100 mL) in a 250 mL flask wrapped in aluminum foil to protect
the contents from light. NBS (1.56 g, 8.75 mmol) was added
into the flask and the reaction mixture was stirred at 25 ꢁC for 2
h. The mixture was partitioned between CH2Cl2 and water and
then the organic phase was collected, dried (MgSO4), and
concentrated under rotary evaporation. The product was
Synthesis of DPAInF
A mixture of 6 (1.55 g, 2 mmol, 1 eq.), diphenylamine (1.69 g,
10 mmol, 5 eq.), Pd(OAc)2 (22.4 mg, 0.1 mmol), NaOtBu (1.15 g,
778 | J. Mater. Chem., 2009, 19, 773–780
This journal is ª The Royal Society of Chemistry 2009