Chemistry of Materials
ARTICLE
126.0, 128.5, 128.8, 129.9, 132.5, 145.5, 145.7; MS (ESI) m/z (rel.
intensity) 491.1 (100) [M þ Na]þ, 467.3 (9) [M ꢀ H]þ; Anal. Calcd.
for C24H20O6S2: C 61.52, H 4.30, S 13.69. Found: C 61.52, H 4.34, S 13.59.
1,5-Bis(trifluoromethylsulfonyloxy)naphthalene (7).56. 1,5-Dihy-
droxynaphthalene (5) (1.00 g, 6.24 mmol) was dissolved in dry pyridine
(30 mL). Trifluoromethanesulfonic anhydride (2.4 mL, 14.36 mmol)
was added at 0 °C. The mixture was left to heat up to room temperature;
then, dry CH2Cl2 (20 mL) was added and the solution was stirred
overnight at room temperature under nitrogen. The reaction was
quenched with saturated aqueous NaHCO3 solution (50 mL), water
was added (100 mL), and the solution was extracted with CH2Cl2 (3 ꢁ
100 mL); the organic phase was dried over MgSO4, filtered, and
evaporated. The residue was purified by column chromatography on
silica gel, eluting with CH2Cl2/hexane (2:1) to afford 7 as a white
powder (2.54 g, 96%): 1H NMR (CDCl3, 500 MHz) δ 7.62 (d, J = 8.5 Hz,
2H), 7.69 (t, J = 8.1 Hz, 2H), 8.14 (d, J = 8.5 Hz, 2H); 13C NMR
(CDCl3, 125 MHz) δ 118.7 (q, JCꢀF = 321.5 Hz), 119.5, 121.5, 127.4,
128.0, 145.5; MS (ESI) m/z (rel. intensity) 447.0 (100) [M þ Na]þ,
425.1 (86) [M ꢀ H]þ; Anal. Calcd. for C12H6F6O6S2: C 33.97, H 1.43,
S 15.11. Found: C 34.47, H 1.79, S 15.11.
9,9-Didodecyl-2-bromofluorene (9). 2-Bromofluorene (8) (8.00 g,
32.6 mmol), 1-bromododecane (16.27 g, 65.3 mmol), and tetrabuty-
lammonium bromide (2.00 g, 6.4 mmol) were dissolved in toluene
(100 mL). NaOH/H2O (50% by weight, 100 mL) was added and the
biphasic mixture was heated at 60 °C under nitrogen for 12 h. The
mixture was allowed to cool to room temperature, and the phases were
separated. The aqueous phase was extracted with hexane (3 ꢁ 200 mL),
the organic layers were combined, dried over MgSO4, and evaporated
under reduced pressure. The excess of 1-bromododecane was removed
from the crude oil by Kugelrohr distillation, and the residue was purified
by column chromatography on silica gel, eluting with hexane to afford
9 as a colorless oil (13.33 g, 70%): 1H NMR (CDCl3, 500 MHz) δ 7.32
(m, 3H), 7.44 (m, 2H), 7.55 (m, 1H), 7.66 (m, 1H); 13C NMR (CDCl3,
125 MHz) δ 14.3, 22.8, 23.8, 29.4, 29.5, 29.7, 29.8, 30.1, 32.1, 40.4, 55.5,
119.9, 121.1, 121.2, 123.0, 126.3, 127.0, 127.6, 130.0, 140.2, 140.3, 150.5,
153.1; MS (ESI) m/z (rel. intensity) 603.4 (97), 604.4 (39), 605.4
(100), 606.4 (38) [M þ Na]þ; Anal. Calcd. for C37H57Br: C 76.39, H
9.88. Found: C 76.47, H 9.57.
afford4asawhitesolid(0.84g, 81%):1HNMR(CDCl3, 500MHz) δ0.69
(m, 8H), 0.86 (t, J = 7.0 Hz, 12H), 1.07 (s, 22H), 1.16ꢀ1.28 (m, 50H),
1.99 (m, 8H), 7.46ꢀ7.48 (m, 4H), 7.56 (s, 2H), 7.58 (d, J = 7.8 Hz, 2H),
7.62 (dd, J = 1.5, 7.9 Hz, 2H), 7.73 (d, J = 7.7 Hz, 2H); 13C NMR (CDCl3,
125 MHz) δ 14.1, 22.7, 23.8, 29.2, 29.3, 29.5, 29.6, 29.6, 29.9, 31.9, 40.2,
55.5, 120.0, 121.0, 121.1, 121.4, 126.2, 126.3, 130.0, 139.3, 139.8, 140.8,
151.1, 153.3; MS (ESI) m/z (rel. intensity) 1181.8 (43), 1182.8 (35),
1183.8 (100), 1184.8 (73), 1185.8 (70), 1186.8 (42), 1187.8 (16) [M þ
Na]þ; Anal. Calcd. for C74H112Br2: C 76.52, H 9.72. Found C 76.64,
H 9.59.
7,70-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-9,9,90,90-tetrakis-
(dodecyl)-2,20-bifluorene (12). 7,70-Dibromo-9,9,90,90-tetrakis(dodecyl)-
2,20-bifluorene (11) (0.83 g, 0.72 mmol), bis(pinacolato)diboron (0.50 g,
1.97 mmol), dry KOAc (0.42 g, 4.29 mmol), and Pd(dppf)Cl2 (0.06 g,
0.07 mmol) were dissolved in dry dioxane (30 mL) under nitrogen
atmosphere. The solution was stirred at 80 °C overnight, filtered, and
evaporated. The residue was purified by column chromatography on silica
gel, eluting withhexanes/ethylacetate(9:1) toafford12 asa light yellow oil
(0.39 g, 43%): 1H NMR (CDCl3, 500 MHz) δ 0.69 (s, 8H), 0.85 (t, J =
7.0 Hz, 12H), 1.05 (s, 22H), 1.15ꢀ1.20 (m, 42H), 1.26 (m, 8H), 1.40 (s,
24H), 2.05 (m, 8H), 7.61 (s, 2H), 7.64 (dd, J = 1.4, 7.8 Hz, 2H), 7.73
(d, J = 7.5 Hz, 2H), 7.77 (s, 2H), 7.79 (d, J = 7.9 Hz, 2H), 7.83 (dd, J = 0.7,
7.6 Hz, 2H); 13C NMR (CDCl3, 125 MHz) δ 14.1, 22.7, 23.8, 24.9, 29.3,
29.3, 29.6, 29.6, 30.0, 31.9, 40.2, 55.2, 83.7, 119.0, 120.3, 121.6, 126.0, 128.9,
133.8, 140.2, 140.9, 143.8, 150.2, 152.1; MS (ESI) m/z (rel. intensity)
1278.2 (100) [M þ Na]þ; Anal. Calcd. for C80H136B2O4: C 82.26,
H 10.92. Found: C 82.11, C 10.85.
Poly(9,9-didodecylfluorene-2,7-diyl-alt-naphthalene-1,5-diyl) (P1).9,9-
Didodecyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)fluorene (2)
(0.27 g, 0.36 mmol), 1,5-bis(trifluoromethylsulfonyloxy)naphthalene
(7) (0.15 g, 0.36 mmol) and Pd(PPh3)4 (0.05 g, 0.04 mmol) were
dissolved in toluene (10 mL). A 1 M aqueous Na2CO3 (3.1 mL,
3.08 mmol) solution was added. The solution was stirred under nitrogen
at 85 °C for 3 days. The mixture was precipitated dropwise in methanol/
water (2:1) and filtered; the precipitate was washed on Soxhlet apparatus
with methanol, then acetone, and extracted with chloroform. The
chloroform fraction was evaporated. The polymer was obtained as a
dark green powder (0.23 g, 95%): 1H NMR (CDCl3, 500 MHz) δ 0.87
(b, 10H), 1.23 (b, 36H), 2.07 (s, 4H), 7.58 (b, 8H), 7.95 (s, 2H), 8.05
(s, 2H); SEC (Da) Mn = 59 735, Mw = 220 990, PDI = 3.7.
9,9,90,90-Tetrakis(dodecyl)-2,20-bifluorene (10). Ni(COD)2 (0.55 g,
1.99 mmol), bipyridine (0.31 g, 1.99 mmol), and COD (0.24 mL,
1.99 mmol) were dissolved under a nitrogen atmosphere and stirred at
75 °C for 30 min. A solution of 9,9-didodecyl-2-bromofluorene (9)
(1.10 g, 1.89 mmol) dissolved in toluene (10 mL) was added. The
reaction was stirred at 80 °C for 24 h. After cooling to room temperature,
5% HCl (50 mL) was added and the mixture was stirred for 1 h. The
product was extracted with Et2O (100 mL), washed with water (3 ꢁ
150 mL), dried over MgSO4, filtered, and evaporated to afford 10 as a
Poly(9,9-didodecylfluorene-2,7-diyl-alt-anthracene-1,5-diyl) (P2).
9,9-Didodecyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)fluorene
(2) (0.11 g, 0.15 mmol) and 1,5-dibromoanthracene (13) (0.05 g,
0.15 mmol) were dissolved in toluene (6 mL). A 1 M aqueous Na2CO3
solution (1.3 mL, 1.29 mmol) was added. Pd(PPh3)4 (20 mg, 17 μmol)
was added, and the reaction mixture was stirred and heated at 95 °C for
3 days under nitrogen. The mixture was cooled to room temperature and
precipitated in methanol (200 mL); the precipitate was filtered, washed
on a Soxhlet apparatus with methanol, then acetone, and extracted
with chloroform. The chloroform fraction was evaporated to afford
1
white powder (0.90 g, 95%): H NMR (CDCl3, 500 MHz) δ 0.71
(m, 8H), 0.86 (t, J = 6.2 Hz, 12H), 1.07 (s, 22H), 1.15ꢀ1.28 (m, 50H),
2.02 (m, 8H), 7.29ꢀ7.33 (m, 3H), 7.35ꢀ7.37 (m, 3H), 7.61 (s, 2H),
7.64 (dd, J = 1.2, 7.9 Hz, 2H), 7.73 (d, J = 7.3 Hz, 2H), 7.77 (d, J = 7.8 Hz,
2H); 13C NMR (CDCl3, 125 MHz) δ 14.1, 22.7, 23.8, 29.3, 29.3, 29.6,
29.6, 30.1, 31.9, 40.4, 55.2, 119.7, 119.8, 121.4, 122.9, 126.0, 126.8, 127.0,
128.7, 140.3, 140.5, 140.8, 151.0, 151.5; MS (ESI) m/z (rel. intensity)
1026.0 (100) [M þ Na]þ; Anal. Calcd. for C74H114: C 88.55, H 11.45.
Found: C 87.45, H 11.41.
1
the polymer as a dark green film (0.09 g, 88%): H NMR (CDCl3,
500 MHz) δ 0.87 (b, 6H), 1.04 (b, 4H), 1.11ꢀ1.37 (m, 36H), 2.12 (b,
4H), 7.50ꢀ7.62 (b, 4H), 7.70 (b, 4H), 7.90 (b, 2H), 8.03 (b, 2H), 8.69
(b, 2H); SEC (Da) Mn = 21 165, Mw = 51 175, PDI = 2.4.
Poly(9,9-didodecylfluorene-2,7-diyl-alt-anthraquinone-1,5-diyl) (P3).
9,9-Didodecyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)fluorene
(2) (0.27 g, 0.36 mmol), 1,5-dichloroanthraquinone (14) (0.10 g,
0.36 mmol), Pd(OAc)2 (4.2 mg, 0.018 mmol), and 2-dicyclohexylpho-
sphino-20,60-dimethoxybiphenyl (15.5 mg, 0.036 mmol) were dissolved
in THF (15 mL). A 0.5 M aqueous Na3PO4 solution (2.2 mL,
1.08 mmol) was added. The solution was stirred and refluxed under
nitrogen overnight; then, a precipitate appeared. THF (15 mL) and
toluene (10 mL) were added. The reaction mixture was stirred at
95 °C for 2 more days, partially evaporated, precipitated dropwise in
7,70-Dibromo-9,9,90,90-tetrakis(dodecyl)-2,20-bifluorene (11). 9,9,90,90-
Tetrakis(dodecyl)-2,20-bifluorene (10) (0.90 g, 0.90 mmol) was dissolved
in CH2Cl2 (15 mL). Br2 (0.32 g, 1.97 mmol) in CH2Cl2 (5 mL) wasadded
at 0 °C under nitrogen. The reaction mixture was left to heat up to room
temperature and stirred for 16 h. A Na2S2O3 solution was added. The
organic phase was extracted with CH2Cl2, washed with water, dried over
MgSO4, filtered, and evaporated. The residue was purified by column
chromatography on silica gel, eluting with hexanes/ethyl acetate (9:1) to
2246
dx.doi.org/10.1021/cm200275v |Chem. Mater. 2011, 23, 2237–2249