Organic Field-Effect Transistors
2-(4-Fluorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was syn-
thesized according to a literature procedure.[16] Material identity
and purity were confirmed by MS and 1H NMR analysis.
Acknowledgements
We gratefully acknowledge the IWT (Institute for the Promotion
of Innovation by Science and Technology in Flanders) for finan-
cial support through the SBO-project 060843 “PolySpec”. We also
acknowledge the European ONE-P project for grant agreement
no. 212311, which facilitates the IMEC-IMOMEC collaboration.
Furthermore, we gratefully thank BELSPO in the frame of the IAP
P6/27 and Phase VII/FS2 networks as well as MINCyT and FRS-
FNRS for supporting the Buenos Aires-Namur scientific coopera-
tion. The computational calculations were performed on the In-
teruniversity Scientific Computing Facility (ISCF) installed at the
Facultꢀs Universitaires Notre-Dame de la Paix (FUNDP, Namur,
Belgium), for which we acknowledge financial support from the
FRS-FRFC (convention no. 2.4.617.07.F), and from the FUNDP. V.L.
thanks the FRS-FNRS for his postdoctoral research position.
N.V.d.B. and W.M. thank the FWO (Fund for Scientific Research-
Flanders) for a doctoral and postdoctoral research mandate, re-
spectively.
4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)benzonitrile was syn-
thesized according to a literature procedure.[16] Material identity
and purity were confirmed by MS and 1H NMR analysis.
2,5-Bis[5’-(4-fluorophenyl)-3’-hexylthiophen-2’-yl]-thiazolo[5,4-d]thia-
zole (4-FC6H4-DTTzTz). General procedure: A solution of 2-(4-fluo-
rophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
(0.480 g,
1.76 mmol) in DME (15 mL) was added dropwise to a stirring mix-
ture of 2,5-bis(5’-bromo-3’-hexylthiophene-2’-yl)thiazolo[5,4-d]thia-
zole (0.450 g, 0.706 mmol) and [Pd(PPh3)4] (0.033 g, 28 mmol) in
DME (20 mL) at ambient temperature. Subsequently, a NaHCO3 so-
lution (1m, 25 mL) was added. After stirring for 24 h at 608C under
N2 and protected from light, the reaction mixture was diluted with
water (50 mL). The organic layer was separated and the aqueous
layer was extracted with CHCl3 (3ꢃ50 mL). The combined organic
layers were washed with a saturated NaHCO3 solution and brine,
dried over MgSO4, and concentrated by evaporation in vacuo. The
reaction product was purified by column chromatography (silica,
eluent hexanes/ethyl acetate 95:5) and recrystallized from ethanol,
resulting in red crystals of pure 4-FC6H4-DTTzTz (0.250 g, 53%).
1H NMR (300 MHz, CDCl3, 258C): d=7.60 (dd, J(H,H)=9/6 Hz, 4H),
7.08 (t, J(H,H)=9 Hz, 4H), 7.12 (s, 2H), 2.94 (t, J(H,H)=8 Hz, 4H),
1.79–1.69 (m, 4H), 1.49–1.43 (m, 4H), 1.37–1.32 (m, 8H), 0.90 ppm
(t, J(H,H)=7 Hz, 6H); 13C NMR (75 MHz, CDCl3, 258C): d=163.6,
161.9, 150.9, 145.2, 144.9, 131.9, 130.7, 128.3 (CH), 127.4 (CH), 116.8
(CH), 32.4 (CH2), 31.1 (CH2), 30.7 (CH2), 30.1 (CH2), 23.3 (CH2),
14.8 ppm (CH3); UV/Vis (CHCl3): lmax (log e)=433 nm (4.714); MS
(ESI): m/z 663 [M+H+].
Keywords: conducting materials · field-effect transistors ·
organic electronics
morphology
· thiazolo[5,4-d]thiazoles · thin film
tron. Rev. 2010, 18, 121; i) A. Operamolla, G. M. Farinola, Eur. J. Org.
[2] a) L. Duan, L. Hou, T.-W. Lee, J. Qiao, D. Zhang, G. Dong, L. Wang, Y. Qiu,
[3] a) H. M. Ko, H. Choi, S. Paek, K. Kim, K. Song, J. K. Lee, J. Ko, J. Mater.
Takacs, G. C. Bazan, A. J. Heeger, Nat. Mater. 2012, 11, 44.
2,5-Bis(3’-hexyl-5’-[4-(trifluoromethyl)phenyl]thiophen-2’-yl)thiazolo-
[5,4-d]thiazole (4-CF3C6H4-DTTzTz). Synthesized according to the
general procedure: 4,4,5,5-tetramethyl-2-[4-(trifluoromethyl)phen-
yl]-1,3,2-dioxaborolane (1.076 g, 3.96 mmol), 2,5-bis(5’-bromo-3’-
hexylthiophene-2’-yl)thiazolo[5,4-d]thiazole (1.00 g, 1.58 mmol),
[Pd(PPh3)4] (0.073 g, 63 mmol), DME (20+80 mL), NaHCO3 (1m,
65 mL); 0.698 g of red crystals (58% yield). 1H NMR (300 MHz,
CDCl3, 258C): d=7.73 (d, J(H,H)=9 Hz, 4H), 7.64 (d, J(H,H)=9 Hz,
4H), 7.27 (s, 2H), 2.97 (t, J(H,H)=8 Hz, 4H), 1.81–1.71 (m, 4H),
1.49–1.45 (m, 4H), 1.38–1.33 (m, 8H), 0.90 ppm (t, J(H,H)=6.9 Hz,
6H); 13C NMR (75 MHz, CDCl3, 258C): d=161.5, 150.9, 144.7, 143.9,
137.3, 133.0, 130.4, 128.3 (CH), 126.6 (CH), 126.2 (CH), 124.7, 32.3
(CH2), 31.2 (CH2), 30.4 (CH2), 30.1 (CH2), 23.3 (CH2), 14.8 ppm (CH3);
UV/Vis (CHCl3): lmax (log e)=434 nm (4.713); MS (ESI): m/z 763 [M+
H+].
708; b) K. Haubner, E. Jaehne, H.-J. P. Adler, D. Koehler, C. Loppacher,
[5] a) S. Ando, J.-I. Nishida, Y. Inoue, S. Tokito, Y. Yamashita, J. Mater. Chem.
2004, 14, 1787; b) S. Ando, J.-I. Nishida, E. Fujiwara, H. Tada, Y. Inoue, S.
5336; d) S. Ando, J.-I. Nishida, E. Fujiwara, H. Tada, Y. Inoue, S. Tokito, Y.
2007, 90, 053506; g) M. Mamada, J.-I. Nishida, D. Kumaki, S. Tokito, Y. Ya-
[6] Naraso, F. Wudl, Macromolecules 2008, 41, 3169–3174.
[7] a) I. Osaka, G. Sauvꢀ, R. Zhang, T. Kowalewski, R. D. McCullough, Adv.
Osaka, R. Zhang, J. Liu, D.-M. Smilgies, T. Kowalewski, R. D. McCullough,
4,4’-[5,5’-(Thiazolo[5,4-d]thiazole-2,5-diyl)-bis(4-hexylthiophene-5,2-
diyl)]dibenzonitrile (4-CNC6H4-DTTzTz). Synthesized according to
the general procedure: 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-
yl)benzonitrile (0.420 g, 1.83 mmol), 2,5-bis(5’-bromo-3’-hexylthio-
phene-2’-yl)thiazolo[5,4-d]thiazole
(0.230 g,
0.367 mmol),
[Pd(PPh3)4] (0.017 g, 15 mmol), DME (20+50 mL), K3PO4 (0.260 g,
1.25 mmol), eluent hexanes/CHCl3 20:80; 0.159 g of red crystals
(64% yield). 1H NMR (300 MHz, CDCl3, 258C): d=7.72 (d, J(H,H)=
9 Hz, 4H), 7.67 (d, J(H,H)=9 Hz, 4H), 7.30 (s, 2H), 2.96 (t, J(H,H)=
7.8 Hz, 4H), 1.80–1.70 (m, 4H), 1.50–1.45 (m, 4H), 1.37–1.32 (m,
8H), 0.90 ppm (t, J(H,H)=6.9 Hz, 6H); 13C NMR (75 MHz, CDCl3,
258C): d=161.6, 151.3, 145.0, 143.5, 138.3, 133.8, 133.5 (CH), 129.2
(CH), 126.6 (CH), 119.3, 112.0, 32.3 (CH2), 31.1 (CH2), 30.5 (CH2), 30.1
(CH2), 23.3 (CH2), 14.8 ppm (CH3); IR (NaCl): nmax =2956/2925/2855
(s, saturated C-H), 2220 cmÀ1 (m, CN); UV/Vis (CHCl3) lmax (log e)=
445 nm (4.777); MS (ESI): m/z 677 [M+H+].
ChemPlusChem 2012, 00, 1 – 9
ꢂ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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