3404
Y. Qiao et al. / Tetrahedron 67 (2011) 3395e3405
3040, 1603 cmꢀ1
.
1H NMR (400 MHz, CDCl3, ppm):
d
8.77 (s, 4H),
method. All materials (3, 5, and 6) were deposited on substrates by
thermal evaporation under a pressure of 4e6ꢂ10ꢀ4 Pa at a de-
8.16 (s, 4H), 8.01 (d, 2H, J¼3.0 Hz), 7.47 (d, 2H, J¼3.0 Hz). 13C NMR
ꢀ1
position rate gradually increased from 0.1 A s to 0.5 A sꢀ1 at the
first 10 nm and then maintained until the thickness of the film was
50 nm. The deposition rate and film thickness were monitored by
ULVAC CRTM-6000. Subsequently, 20 nm thick gold source and
drain electrodes were deposited on the films via a shadow mask.
The channel length and width were 0.11 mm and 5.30 mm, re-
spectively. The FET characteristics were measured at room tem-
perature in air using Keithley 4200 SCS.
ꢀ
ꢀ
(100 MHz, CDCl3, ppm):
d 168.7, 144.1, 131.9, 131.6, 128.4, 125.3,
123.3, 119.6. MS (EI, m/z): 368 (Mþ). Anal. Calcd for C22H12N2S2: C,
71.71; H, 3.28; N, 7.60. Found: C, 71.62; H, 3.30; N, 7.45.
4.2.3. 2,7-Diphenyl-4,5,9,10-tetrahydro-pyrene (DPh-P, 5). Pale
yellow powders (0.56 g, 39%); mp 316 ꢁC; IR (KBr) 3039, 1770,
1598 cmꢀ1. 1H NMR (400 MHz, CDCl3, ppm):
d 8.41 (s, 4H), 8.16 (s,
4H), 7.90 (d, 4H, J¼7.5 Hz), 7.57 (t, 4H, J¼7.6 Hz), 7.45 (t, 2H,
J¼7.4 Hz). 13C NMR (100 MHz, CDCl3, ppm):
d 141.7, 139.2, 131.7,
129.1, 128.2, 128.1, 127.6, 124.1, 124.0. MS (EI, m/z): 354 (Mþ). Anal.
4.5. Physicochemical studies
Calcd for C28H18: C, 94.88; H, 5.12. Found: C, 94.48; H, 5.14.
UVevis spectra were recorded on a JASCO V-570 spectrometer.
Cyclic voltammetry (CV) measurements were carried out on
a CHI660C analyzer in a conventional three-electrode cell setup with
Pt button as the working electrode, a platinum wire as the counter
electrode, Ag/AgCl as the reference electrode and calibrated with
ferrocene/ferrocenium (Fc/Fcþ) as an external potential marker in
anhydrous CH2Cl2 solution containing 0.1 M nBu4NPF6 as a sup-
porting electrolyte at a scan rate of 100 mV sꢀ1 under a nitrogen
atmosphere at room temperature. Thermal gravimetric analysis
(TGA) was performed on a Shimadzu DTG 60 instrument. X-ray
diffraction (XRD) measurements of thin films were performed in
4.2.4. 2,7-Di-(5-hexylthiophen-2-yl)-4,5,9,10-tetrahydro-pyrene
(DHT-P, 6). Yellow powders (0.56 g, 26%); mp 228 ꢁC; IR (KBr)
3032, 2961, 2870, 2846, 1600 cmꢀ1. 1H NMR (400 MHz, CDCl3, ppm)
d
8.32 (s, 4H), 8.05 (s, 4H), 7.42 (d, 2H, J¼3.4 Hz), 6.86 (d, 2H,
J¼3.1 Hz), 2.90 (t, 4H, J¼7.6 Hz), 1.81e1.73 (m, 4H), 1.47e1.43 (m,
4H), 1.36e1.35 (m, 8H), 0.92 (t, 6H, J¼6.5 Hz). 13C NMR (100 MHz,
CDCl3, ppm):
d 146.7, 142.1, 132.6, 131.6, 128.0, 125.5, 123.9, 123.6,
122.3, 31.8, 31.7, 30.5, 29.0, 22.8, 14.2. MS (EI, m/z): 534 (Mþ). Anal.
Calcd for C36H38S2: C, 81.38; H, 7.19. Found: C, 81.06; H, 7.16.
4.3. X-ray crystallographic analysis
reflection mode at 40 kV and 200 mA with Cu Ka radiation using
a 2 kW Rigaku X-ray diffractometer. Atomic force microscopy (AFM)
images of the thin films were obtained on a Nanoscope IIIa AFM
(Digital Instruments) operating in tapping mode.
X-ray crystallographic data were collected with a Bruker Smart
CCD diffractometer through using graphite-monochromated Mo K
a
ꢀ
radiation (l¼0.71073 A). The data were collected at 173 K for
compounds 4e6, whereas the data for compound 3 was collected at
153 K. The structures were resolved by the direct method and re-
fined by full-matrix least-squares on F2. The computation was
performed with the SHELXL-97 program. All non-hydrogen atoms
were refined anisotropically. CCDC 808315 (DT-P), 808316 (DTz-P),
808317 (DPh-P), and 808318 (DHT-P) contain the supplementary
crystallographic data for this paper. These data can be obtained free
of charge from The Cambridge Crystallographic Data Centre via
Acknowledgements
The authors acknowledge the financial support from National
Natural Science Foundation of China (21021091, 20952001), Min-
istry of Science and Technology of China, and Chinese Academy of
Sciences.
Supplementary data
Crystallographic
data
for
DT-P
(3):
crystal
size:
3
ꢀ
0.30ꢂ0.06ꢂ0.04 mm ; monoclinic; C2/c; Z¼4; a¼21.662 (4) A,
3
ꢀ
These data include TGA and DSC for compounds 3e6, X-ray
crystallographic analyses for compounds 3 (CCDC 808315), 4 (CCDC
808316), 5 (CCDC 808317), 6 (CCDC 808318), OFETs characteristic
curves for compound 3, 5, and 6, copies of 1H and 13C NMR spectra
and for compounds 3e6. Supplementary data related to this article
ꢀ
ꢀ
b¼4.0056 (8) A, c¼21.773 (4) A; V¼1673.5 (6) A ; rcalculated
¼
1.455 g cmꢀ3; of 6396 reflections, 2003 were unique; GOF¼1.124;
132 parameters; R1¼0.0638, wR2¼0.1516 (for all reflections).
Crystallographic data for DTz-P (4): 0.30ꢂ0.20ꢂ0.05 mm3;
ꢀ
ꢀ
monoclinic; P2(1)/n; Z¼2; a¼3.8727 (8) A, b¼20.191 (4) A,
c¼10.540 (2) A; V¼812.9 (3) A ; rcalculated¼1.505 g cmꢀ3; of 6446
reflections, 1828 were unique; GOF¼1.180; 155 parameters;
R1¼0.0871, wR2¼0.1639 (for all reflections).
3
ꢀ
ꢀ
References and notes
Crystallographic data for DPh-P (5): 0.29ꢂ0.27ꢂ0.24 mm3; or-
ꢀ
ꢀ
thorhombic; Pbca; Z¼4; a¼7.7673 (16) A, b¼7.6033 (15) A,
1. Kelley, T. W.; Baude, P. F.; Gerlach, C.; Ender, D. E.; Muyres, D.; Haase, M. A.;
Vogel, D. E.; Theiss, S. D. Chem. Mater. 2004, 16, 4413.
2. Mas-Torrent, M.; Rovira, C. Chem. Soc. Rev. 2008, 37, 827.
3. Allard, S.; Forster, M.; Souharce, B.; Thiem, H.; Scherf, U. Angew. Chem., Int. Ed.
2008, 47, 4070.
4. Tsumura, A.; Koezuka, H.; Ando, T. Appl. Phys. Lett. 1986, 49, 1210.
5. Chen, J. L.; Leblanc, V.; Kang, S. H.; Benning, P. J.; Schut, D.; Baldo, M. A.;
Schmidt, M. A.; Bulovic, V. Adv. Funct. Mater. 2007, 17, 2722.
6. Dimitrakopoulos, C. D.; Malenfant, P. R. L. Adv. Mater. 2002, 14, 99.
7. Forrest, S. R. Chem. Rev. 1997, 97, 1793.
c¼30.732 (6) A; V¼1815.0 (6) A ; rcalculated¼1.297 g cmꢀ3; of 10,002
reflections, 1647 were unique; GOF¼1.348; 127 parameters;
R1¼0.0743, wR2¼0.1818 (for all reflections).
3
ꢀ
ꢀ
Crystallographic data for DHT-P (6): 0.37ꢂ0.29ꢂ0.10 mm3; tri-
ꢀ
ꢀ
ꢀ
clinic; Pe1; Z¼1; a¼5.727 (2) A, b¼7.821 (4) A, c¼16.117 (7) A;
3
V¼699.5 (5) A ; rcalculated¼1.270 g cmꢀ3; of 9284 reflections, 3185
were unique; GOF¼1.079; 173 parameters; R1¼0.0562, wR2¼0.1314
(for all reflections).
ꢀ
8. Coropceanu, V.; Cornil, J.; da Silva, D. A.; Olivier, Y.; Silbey, R.; Bredas, J. L. Chem.
Rev. 2007, 107, 926.
9. Murphy, A. R.; Frechet, J. M. J. Chem. Rev. 2007, 107, 1066.
10. Zaumseil, J.; Sirringhaus, H. Chem. Rev. 2007, 107, 1296.
11. Baca, A. J.; Ahn, J. H.; Sun, Y. G.; Meitl, M. A.; Menard, E.; Kim, H. S.; Choi, W. M.;
Kim, D. H.; Huang, Y.; Rogers, J. A. Angew. Chem., Int. Ed. 2008, 47, 5524.
12. Voss, D. Nature 2000, 407, 442.
13. Crone, B.; Dodabalapur, A.; Lin, Y. Y.; Filas, R. W.; Bao, Z.; LaDuca, A.; Sarpeshkar,
R.; Katz, H. E.; Li, W. Nature 2000, 403, 521.
14. Mitschke, U.; Bauerle, P. J. Mater. Chem. 2000, 10, 1471.
15. Andersson, P.; Forchheimer, R.; Tehrani, P.; Berggren, M. Adv. Funct. Mater. 2007,
17, 3074.
4.4. FET device fabrication and measurement
OFET devices based on vacuum-deposited thin films were fab-
ricated in a top-contact device configuration. The heavily doped
n-type Si wafer with a 500 nm-thick SiO2 layer and a capacitance of
7.5 nF cmꢀ2 was used as the substrate. The gate dielectric was
treated with octadecyltrichlorosilane (OTS) by a vapor deposition