Journal of Materials Chemistry C
Paper
performed: (a) with phenylboronic acid pinacol ester (0.05 g, (m, 24H, 12 ꢁ CH
2
), 1.00–0.40 (m, 18H, 6 ꢁ CH
C NMR (75.45 MHz, CDCl : CF COOD = 30 : 1 v/v, d): 167.7
.12 mmol, 2 h reflux). After cooling, the reaction mixture (2 ꢁ CQO), 167.3 (2 ꢁ CQO), 146.4, 145.3, 142.5, 139.4, 138.6,
3
) (Fig. S12, ESI†).
1
3
0
.25 mmol, 1 h reflux) and (b) with 2-ethylhexyl bromide (0.2 ml,
3
3
1
was separated into two layers. Water layer (aq. Na CO , bottom) 136.1, 133.3, 132.0, 130.3, 125.4, 124.4, 122.7, 119.0, 115.2,
2
3
was wasted and organic layer (crude polymer in THF, upper) was 112.4, 111.4 (32C aromatic), 47.6 (Cz-N–C), 42.3, 40.7, 33.4,
poured into an excess of methanol (700 mL). The precipitate was 32.4, 31.3, 26.6, 25.7, 23.3, 16.7, 16.5, 13.2 (24C aliphatic)
filtered off (S3), washed with water and methanol, and dried. (Fig. S13, ESI†). FTIR (ATR): 2959, 2926, 2860, 1698, 1653,
The raw material was dissolved in chloroform, filtered through 1588, 1456, 1431, 1402, 1322, 1242, 1180, 1121, 1088, 1030,
s
ꢀ1
a short column of Celite 577/aluminum oxide/silica gel 60 998, 860, 808, 750, 713, 626, cm (Fig. S21, ESI†).
ca. + 4 ꢁ 3/3/3 cm) and the volume was reduced to ca. 15–20 mL
by a rotary evaporator. The solution was precipitated into methanol
700 mL), the purified dark red polymer was filtered off (S3) and
dried to a constant weight (yield: Y). The synthesized D–A polymers
were characterized by SEC (M , M , Ð, P) in chloroform (Table 1)
(
1
CHDCz-DDPDI. Y = 0.3301 g (67%); H NMR (300.13 MHz,
CDCl :CF COOD = 20:1 v/v, d): 9.10–7.25 (m, 12H, aromatic H),
.55 (br s, 1H, Cz-N–CHQ), 4.17 (br s, 4H, 2 ꢁ N–CH
+ 2 ꢁ N–C–CH
m, 8H, Cz-N–Cz (CH ), 1.50–0.90 (m, 60H,
), 0.90–0.50 (m, 12H, 4 ꢁ CH
: CF COOD = 20 : 1 v/v, d): 167.6
(
3
3
4
(
3
2
), 2.60–1.55
2
)
2
2
w
n
1
3
1
13
0 ꢁ CH
2
3
) (Fig. S14, ESI†).
C
and by H and C NMR, and FTIR spectroscopy.
NMR (75.45 MHz, CDCl
3
3
1
CFC8-DDPDI. Y = 0.3285 g (68%); H NMR (300.13 MHz (2 ꢁ CQO), 167.1 (2 ꢁ CQO), 146.6, 145.5, 142.6, 138.8,
CDCl
4
2
3
:CF
3
COOD = 20:1 v/v, d): 8.90–7.30 (m, 12H, aromatic H), 136.4, 133.4, 132.1, 130.4, 125.2, 124.4, 124.0, 122.7, 118.9,
), 2.20–1.55 (br d, 8H, 2 ꢁ fluorene–CH
115.2, 111.4 (32C aromatic), 56.6 (Cz-N–Cz), 44.2, 36.4, 34.6,
), 1.50–0.45 (m, 72H, 30 ꢁ CH + 4 ꢁ CH ), (Fig. S6, 34.5, 32.3–32.1, 30.8–29.8, 25.4, 25.3, 16.8, 16.6 (40C aliphatic)
.16 (br s, 4H, 2 ꢁ N–CH
2
2
+
ꢁ N–C–CH
2
2
3
1
3
ESI†). C NMR (75.45 MHz, CDCl :CF COOD = 20:1 v/v, d): 167.7 (Fig. S15, ESI†). FTIR (ATR): 2918, 2853, 1698, 1654, 1585, 1453,
3
3
(
1
2 ꢁ CQO), 167.0 (2 ꢁ CQO), 156.2, 145.1, 144.0, 138.7, 136.3, 1431, 1400, 1326, 1245, 1162, 1125, 1074, 1023, 994, 860, 810,
ꢀ1
33.4, 132.1, 130.5, 125.4, 124.4, 122.7, 118.9, 115.2, 111.4 (32C 738, 717, 640, cm (Fig. S22, ESI†).
), 44.2, 42.8, 34.7, 32.4–32.1, 30.8, 29.8,
6.7, 25.4, 16.8 (40C aliphatic), (Fig. S7, ESI†). FTIR (ATR): 2922,
852, 1698, 1660, 1588, 1460, 1431, 1402, 1326, 1245, 1162, CDCl
aromatic), 58.8 (Q C(octyl)
2
2
1
2
1
CHDCz-EHPDI. Y = 0.2990 g (68%); H NMR (300.13 MHz,
:CF COOD = 60:1 v/v, d): 9.05–7.27 (m, 12H, aromatic H),
4.60 (br s, 1H, Cz-N–CHQ), 4.14 (br s, 4H, 2 ꢁ N–CH ), 2.25 (br s,
H, 2 ꢁ QCH–), 1.93 (br s, 4H, Cz-N–Cz (CH ) ), 1.60–0.95
3
3
ꢀ
1
125,1074, 1023, 860, 815, 760, 710, 625, cm (Fig. S18, ESI†).
2
2
(
2
2
1
CFC8-EHPDI. Y = 0.2275 g (52%); H NMR (300.13 MHz,
CDCl
, d): 8.80–7.27 (m, 12H, aromatic H), 4.13 (br s, 4H, 2 ꢁ N–
m, 40H, 20 ꢁ CH
2
), 0.88 (s, 12H, 4 ꢁ CH
3
), 0.80–0.55 (br d, 6H,
1
3
3
2
ꢁ CH
) (Fig. S16, ESI†). C NMR (75.45 MHz, CDCl :CF COOD =
3
3
3
CH ), 2.15–1.75 (br d, 6H, 2 ꢁ fluorene–CH + 2 ꢁQCH–), 1.60–
2
2
60 : 1 v/v, d): 165.1 (2 ꢁ CQO), 164.5 (2 ꢁ CQO), 144.2, 142.7,
140.6, 140.1, 136.7, 136.0, 133.6, 130.6, 128.9, 127.8, 122.5, 121.9,
120.2, 116.4, 112.6, 108.8 (32C aromatic), 56.9 (Cz-N–Cz), 45.0,
1
2
.00 (m, 40H, 20 ꢁ CH ), 0.88 (br s, 12H, 4 ꢁ CH ), 0.75 (br s, 6H,
2
3
13
ꢁ CH ) (Fig. S8, ESI†). C NMR (75.45 MHz, CDCl , d): 164.0
3
3
(
2 ꢁ CQO), 163.5 (2 ꢁ CQO), 153.4, 142.7, 142.0, 141.7, 141.0,
3
1
2
8.0, 33.8, 31.9, 30.8, 29.8, 29.5, 29.3, 28.7, 26.9, 24.0, 23.1, 22.7,
5.1, 14.1, 10.7 (32C aliphatic) (Fig. S17, ESI†). FTIR (ATR): 2951,
925, 2857, 1698, 1654, 1588, 1456, 1431, 1402, 1322, 1242, 1180,
1
1
3
35.2, 134.6, 132.8, 130.4, 129.6, 129.1, 128.0, 127.5, 123.6, 122.5,
22.3 (32C aromatic), 56.3 (Q C(octyl) ), 44.6, 40.4, 38.3, 31.9, 31.1,
0.8, 30.3, 30.1, 29.8, 29.4, 29.0, 24.4, 23.2, 22.7, 14.1, 10.8
2
ꢀ
1
1125, 1088, 1030, 998, 863, 808, 742, 713, 640, cm (Fig. S23, ESI†).
(32C aliphatic) (Fig. S9, ESI†). FTIR (ATR): 2926, 2850, 1701,
1
661, 1588, 1456, 1435, 1402, 1325, 1242, 1180, 1129, 1088,
ꢀ
1
Conclusions
1030, 862, 812, 753, 713, 629, cm (Fig. S19, ESI†).
0
1
Six D–A copolymers containing N,N -dialkylperylene-3,4,9,10-tetra-
carboxydiimide A units and three different D units [9,9-dioctyl-
fluorene, 9-(2-ethylhexyl)carbazole or 9-(heptadecan-9-yl)carbazole],
CEHCz-DDPDI. Y = 0.2530 g (58%); H NMR (300.13 MHz,
CDCl :CF COOD = 30 : 1 v/v, d): 9.00–7.25 (m, 12H, aromatic H), 4.19
br s, 6H, 3 ꢁ N–CH ), 1.69 (br s, 5H, 1 ꢁQCH– + 2 ꢁ N–C–CH ),
3
3
(
1
2
2
0
namely, poly[N,N -dialkylperylene-3,4,9,10-tetracarboxydiimide-
.55–0.95 (m, 44H, 22 ꢁ CH
2
), 0.90–0.40 (m, 12H, 4 ꢁ CH
:CF COOD = 30:1 v/v, d): 167.7
2 ꢁ CQO), 167.3 (2 ꢁ CQO), 145.5, 142.6, 139.4, 138.9, 138.4,
36.4, 133.4, 132.1, 130.4, 129.8, 125.6, 124.4, 123.9, 122.7, 118.9,
15.1, 112.4, 111.4 (32C aromatic), 50.3 (Cz-N–C), 44.2, 42.4, 34.7,
3.7, 32.5–30.8, 29.8, 27.2, 25.6, 25.4, 16.8, 16.6, 13.4 (32C aliphatic)
Fig. S11, ESI†). FTIR (ATR): 2918, 2853, 1698, 1658, 1581, 1460, 1435,
406, 1326, 1245, 1162, 1121, 1074, 1023, 998, 859, 808, 764, 746, 713,
3
) (Fig. S10,
13
1,7-diyl-alt-9-alkylcarbazole-2,7-diyl or 9,9-dioctylfluorene-2,7-
diyl]s, were synthesized by Suzuki coupling and characterized
by elemental analysis, NMR, IR and SEC. They exhibited very
good thermal stability in nitrogen and in air, indicating good
oxidation stability, which is important for their applications.
Contrary to the well-resolved absorption and PL spectra of the
PDI unit in solutions, the absorption spectra and PL spectra of
the copolymers, both in solutions and as thin films, consisted
of broad bands in the visible spectral region corresponding
ESI†). C NMR (75.45 MHz, CDCl
3
3
(
1
1
3
(
1
6
ꢀ
1
25, cm (Fig. S20, ESI†).
1
CEHCz-EHPDI. Y = 0.2510 g (65%); H NMR (300.13 MHz, to the p–p* transitions of the conjugated backbone. The PL
CDCl :CF COOD = 30:1 v/v, d): 9.05–7.27 (m, 12H, aromatic H), maxima in thin films were redshifted when compared with those
.16 (br s, 6H, 3 ꢁ N–CH ), 1.93 (br s, 3H, 3 ꢁQCH–), 1.65–1.00 in the solution spectra, which corresponds to the backbone
3
3
4
2
14690 | J. Mater. Chem. C, 2019, 7, 14678--14692
This journal is ©The Royal Society of Chemistry 2019