1H NMR (CDCl3): d 0.87 (t, 6 H), 1.15–1.47 (m, 36 H), 1.79
(t, 4 H), 4.10 (t, 4 H), 7.28–7.31 (s, 1H), 7.52–7.70 (dd, 2 H), 7.86
(s, 1H), 8.05 (d, 2 H), 8.80–9.00 (dd, 2 H). 13C NMR (CDCl3):
161.25, 144.93, 140.88, 138.49, 136.04, 135.77, 135.74, 135.57,
135.35, 135.28, 135.24, 132.92, 132.59, 131.69, 131.15, 131.01,
130.79, 129.67, 128.70, 128.01, 126.55, 126.49, 125.87, 124.37,
121.80, 121.66, 108.98, 108.05, 107.83, 42.33, 31.88, 29.93, 29.66,
29.59, 29.57, 29.54, 29.52, 29.21, 26.81, 22.64, 14.04.
2 (a) A. Facchetti, Mater. Today, 2007, 10, 28; (b) M. M. Ling and
Z. Bao, Chem. Mater., 2004, 16, 4824; (c) A. Facchetti,
M. H. Yoon, C. L. Stern, G. R. Hutchison, M. A. Ratner and
T. J. Marks, J. Am. Chem. Soc., 2004, 126, 13480; (d) J. A. Merlo,
C. R. Newman, C. P. Gerlach, T. W. Kelley, D. V. Muyres,
S. E. Fritz, M. T. Toney and C. D. Frisbie, J. Am. Chem. Soc.,
2005, 127, 3997; (e) Z. Bao, A. J. Lovinger and A. Dodabalapour,
Adv. Mater., 1997, 9, 42; (f) H. Meng, Z. Bao, A. J. Lovinger,
B. C. Wang and A. M. Mujsce, J. Am. Chem. Soc., 2001, 123, 9214;
(g) V. Podzorov, S. E. Sysoev, E. Loginova, V. M. Pudalov and
M. E. Gershenson, Appl. Phys. Lett., 2003, 83, 3504; (h) H. Meng,
F. Sun, M. B. Goldfinger, G. D. Jaycox, Z. Li, W. J. Marshall and
G. S. Blackman, J. Am. Chem. Soc., 2005, 127, 2406; (i) T. Siegrist,
R. M. Fleming, R. C. Haddon, R. A. Laudise, A. J. Lovinger,
H. E. Katz, P. Bridenbaugh and D. D. Davis, J. Mater. Res., 1995,
10, 2170; (j) X. C. Li, H. Sirringhaus, F. Garnier, A. B. Holmes,
S. C. Moratti, N. Feeder, W. Clegg, S. J. Teat and R. H. Friend,
J. Am. Chem. Soc., 1998, 120, 2206.
Calculated for C54H60F12N2O2S2: C 61.12, H 5.70, F 21.48, N
2.64, O 3.02, S 6.04%; Found: C 61.08, H 5.68, N 2.57, S 6.10%.
MS (MALDI-TOF) m/z 1060.73 (M). calcd. for
C54H60F12N2O2S2 ¼ 1060.39.
4.3.4. Synthesis of F3PDPP. Dibromo-DD-DPP compound
(0.300 g, 0.37 mmol), 3,4,5-trifluorophenylboronic acid (0.243 g,
0.945 mmol, 2.5 eq.) and Pd(PPh3)4 (30mg, 0.025 mmol) were
added to a 50 mL Schlenk flask and subjected to three vacuum/
argon refill cycles. Argon degassed toluene (15 mL), aqueous 2M
K2CO3 (7 mL) and ethanol (3 mL) were added to the above
mixture and stirred for 20 min under argon. After three vacuum/
argon cycles the mixture was heated at 80 ꢁC for 24 h then
monitored via TLC. After completion of the reaction, solvent
was removed on rotovap and the product extracted with chlo-
roform, then successively washed with water, and dried over
MgSO4. Removal of the solvent afforded the crude product
which was then purified using column chromatography (silica
gel, chloroform as eluent) and gave the product as a dark purple
crystalline solid (0.240 g, 72%).
3 (a) G. Li, V. Shrotriya, J. S. Huang, Y. Yao, T. Moriarty, K. Emery
and Y. Yang, Nat. Mater., 2005, 4, 864; (b) G. Dennler,
C. Lungenschmied, H. Neugebauer, N. S. Sariciftci and
A. Labouret, J. Mater. Res., 2005, 20, 3224; (c) G. Yu, J. Gan,
J. C. Hummelen, F. Wudl and A. J. Heeger, Science, 1995, 270,
1789; (d) J. Liu, E. N. Kadnikova, Y. Liu, M. McGehee and
ꢁ
J. M. J. Freechet, J. Am. Chem. Soc., 2004, 126, 9486; (e) F. Yang,
M. Shtein and S. R. Forrest, Nat. Mater., 2005, 4, 37;
€
€
(f) L. Schmidt-Mende, A. Fechtenkootter, K. Mullen, E. Moons,
R. H. Friend and J. D. MacKenzie, Science, 2001, 293, 1119;
(g) L. Tan, M. D. Curtis and A. H. Francis, Chem. Mater., 2003,
15, 2272; (h) A. J. Breeze, A. Salomn, D. S. Ginley, B. A. Gregg,
€
H. Tillmann and H. H. Hoorhold, Appl. Phys. Lett., 2002, 81, 3085;
(i) P. Peumans, S. Uchida and S. R. Forrest, Nature, 2003, 425, 158;
(j) C. W. Tang, Appl. Phys. Lett., 1986, 48, 183.
4 (a) Y. Shirota and H. Kageyama, Chem. Rev., 2007, 107, 953;
(b) H. Klauk, Organic Electronics: Materials Manufacturing and
Applications; Wiley: Weinheim, 2006; (c) H. Inokuchi, Org.
Electron., 2006, 7, 62; (d) J. Locklin, M. Roberts, S. Mannsfeld and
Z. Bao, Polym. Rev., 2006, 46, 79; (e) J. Zaumseil and
H. Sirringhaus, Chem. Rev., 2007, 107, 1296.
1H NMR (CDCl3): d 0.87 (t, 6 H), 1.10–1.47 (m, 36 H), 1.78
(t, 4 H), 4.10 (t, 4 H), 7.25 (d, 4 H), 7.40 (d, 2 H), 8.87 (d, 2 H). 13
C
NMR (CDCl3): 161.27, 139.30, 136.31, 130.04, 125.80, 110.48,
110.32, 110.25, 108.66, 87.53, 73.04, 66.83, 42.31, 37.01, 31.87,
29.98, 29.60, 29.58, 29.55, 29.49, 29.30, 29.22, 26.86, 22.63, 14.03.
Calculated for C50H58F6N2O2S2: C 66.94, H 6.52, F 12.71, N
3.12, O 3.57, S 7.15%; Found: C 66.88, H 6.46, N 3.02, S 7.02%.
MS (MALDI-TOF) m/z 896.24 (M). calcd. for
C50H58F6N2O2S2 ¼ 896.38.
5 (a) C. J. Brabec, N. S. Sariciftici and J. C. Hummelen, Adv. Funct.
€
Mater., 2001, 11, 15; (b) S. Gunes, H. Neugebauer and
N. S. Sariciftci, Chem. Rev., 2007, 107, 1324; (c) A. J. Heeger,
J. Phys. Chem. B, 2001, 105, 8475; (d) N. S. Sariciftici and
A. J. Heeger, in Handbook of Organic Conducting Molecules and
Polymer, Vol. 1 (Ed. H. S. Nalwa), Wiley, New York 1997.
6 W. Ma, C. Yang, X. Gong, K. Lee and A. J. Heeger, Adv. Funct.
Mater., 2005, 15, 1617.
8 (a) Y. F. Li and Y. P. Zhou, Adv. Mater., 2008, 20, 2952;
(b) H. E. Katz, Z. Bao and S. L. Gilat, Acc. Chem. Res., 2001, 34,
359; (c) H. S. O. Chan and S. C. Ng, Prog. Polym. Sci., 1998, 23,
1167; (d) M. Thelakkat, Macromol. Mater. Eng., 2002, 287,
442.
9 (a) N. C. Greenham, S. C. Moratti, D. D. C. Bradley, R. H. Friend
and A. B. Holmes, Nature, 1993, 365, 628; (b) G. Hughes and
M. R. Bryce, J. Mater. Chem., 2005, 15, 94.
10 N. S. Sariciftci, L. Smilowitz, A. J. Heeger and F. Wudl, Science,
1992, 258, 1474.
11 (a) T. Kietzke, H.-H. Horhold and D. Neher, Chem. Mater., 2005, 17,
6532; (b) S. C. Veenstra, J. Loos and J. M. Kroon, Progr. Photovolt.:
Res. Appl., 2007, 15, 727.
5. Acknowledgements
The authors acknowledge the Visiting Investigatorship Pro-
gramme (VIP) of the Agency for Science, Technology and
Research (A*STAR), Republic of Singapore for financial
support. We are also thankful to Chua Pei Lin and Pang Lusha
from republic polytechnic, Singapore for scaling up of some
starting precursors during their attachment program with
IMRE.
12 A. M. Ballantyne, L. Chen, J. Dane, T. Hammant, F. M. Braun,
M. Heeney, W. Duffy, I. McCulloch, D. D. C. Bradley and
J. Nelson, Adv. Funct. Mater., 2008, 18, 2373.
6. References
13 M. M. Mandoc, F. B. Kooistra, J. C. Hummelen, B. de Boer and
P. W. M. Blom, Appl. Phys. Lett., 2007, 91, 263505.
1 (a) J. Kido and Y. Okamoto, Chem. Rev., 2002, 102, 2357;
(b) J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks,
K. Mackay, R. H. Friend, P. L. Burns and A. B. Holmes, Nature,
1990, 347, 539; (c) C. W. Tang and S. A. VanSlyke, Appl. Phys.
Lett., 1987, 51, 913; (d) D. Braun and A. J. Heeger, Appl. Phys.
Lett., 1991, 58, 1982; (e) R. H. Friend, R. W. Gymer,
A. B. Holmes, J. H. Burroughes, R. N. Marks, C. Taliani,
14 (a) R. Y. C. Shin, T. Kietzke, S. Sudhakar, A. Dodabalapur,
Z.-K. Chen and A. Sellinger, Chem. Mater., 2007, 19, 1982;
(b) Z. E. Ooi, T. L. Tam, R. Y. C. Shin, Z. K. Chen, T. Kietzke,
A. Sellinger, M. Baumgarten, K. Mullen and J. C. deMello,
J. Mater. Chem., 2008, 18, 4619; (c) R. Y. C. Shin, P. Sonar,
P. S. Siew, Z.-K. Chen and A. Sellinger, J. Org. Chem., 2009, 74, 3293.
15 Unpublished results.
ꢁ
€
D. D. C. Bradley, D. A. Dos Santos, J. L. Bredas, M. Logdlund
and W. R. Salaneck, Nature, 1999, 397, 121; (f) A. P. Kulkarni,
C. J. Tonzola, A. Babel and S. A. Jenekhe, Chem. Mater., 2004, 16,
4556.
16 Y. F. Lim, Y. Shu, S. R. Pankin, J. E. Anthony and G. Malliaras,
J. Mater. Chem., 2009, 19, 3049.
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