The Journal of Organic Chemistry
ARTICLE
-[4-(2,7-Dimethoxy-9H-carbazol-9-yl)phenyl]-5-(2,4,6-trimethyl-
phenyl)-1,3,4-oxadiazole (5h). Followingtheprocedure for5a, 4f(0.07g,
0.2 mmol), 2,7-dimethoxycarbazole(0.07g, 0.3mmol), K2CO3 (200 mg),
and DMSO (10 mL), with recrystallization of the product from acetoni-
trile. gave 5h (0.05 g, 50%) as colorless crystals. Mp: 186.3ꢀ187.2 °C.
Anal. Calcd for C32H29N3O3: C, 76.32; H, 5.80; N, 8.34. Found: C, 76.27;
H, 5.85; N, 8.40. δH (500 MHz, CDCl3) 8.28 (1H, s), 8.16 (1H, d, J 9.8),
7.94 (2H, d, J 8.5), 7.56 (1H, d, J 8.1), 7.05 (2H, s), 6.90 (2H, dd, J 3.3,
9.5), 6.49 (2H, d, J 2.2), 3.82 (6H, s), 2.40 (3H, s), 2.38 (6H, s), 2.14
(3H, s). δC (126 MHz, CDCl3) 164.7, 164.5, 158.7, 142.4, 141.5, 139.4,
139.0, 138.9, 130.4, 129.2, 126.2, 124.6, 121.2, 120.6, 117.5, 108.6, 94.3,
55.9, 21.6, 20.8, 18.2. MS (ASAP+): m/z 504.2 (M+H+, 100%).
2-[4-(2,7-Dimethoxy-9H-carbazol-9-yl)phenyl]-5-(2,4,6-triisopropyl-
phenyl)-1,3,4-oxadiazole (5i). Following the procedure for 5a, 4c (0.2 g,
0.5 mmol), 2,7-dimethoxycarbazole (0.2 g, 1.2 mmol), K2CO3 (400 mg),
and DMSO (20 mL), with recrystallization of the product from acetoni-
trile, gave 5i (0.17 g, 60%) as colorless crystals. Mp: 192.5ꢀ194.0 °C.
Anal. CalcdforC37H39N3O3: C, 77.46; H, 6.85; N, 7.32. Found:C, 77.35;
H, 6.93; N, 7.35. δH (500 MHz, CDCl3) 8.36 (2H, d, J 8.5), 7.93 (2H, d,
J 9.2), 7.77 (2H, d, J 8.5), 7.18 (2H, s), 6.97ꢀ6.88 (4H, m), 3.86 (6H, s),
3.01 (1H, dt, J 7.0, 13.9), 2.79ꢀ2.67 (2H, m), 1.34 (6H, d, J 6.9), 1.28
(12H, d, J 6.8). δC (126 MHz, CDCl3) 164.7, 164.4, 158.7, 152.8, 149.8,
142.0, 141.1, 128.9, 127.6, 123.1, 121.5, 120.6, 119.8, 118.0, 108.9, 94.6,
56.0, 34.9, 31.8, 24.4, 24.2. MS (ASAP+): m/z 574.3 (M+H+, 100%).
2-[4-(9H-Carbazol-9-yl)phenyl]-5-methyl-1,3,4-oxadiazole (7a). Fol-
lowing the procedure for 5a, 6 (0.50 g, 2.8 mmol), carbazole (0.47 g, 2.8
mmol), K2CO3 (1.9 g), and DMSO (40 mL) with elution of the product
with dichloromethane followed by recrystallization from acetonitrile gave 7a
(0.55 g, 61%) as colorless crystals. Mp: 202.8ꢀ203.8 °C. Anal. Calcd for
C21H15N3O: C, 77.52; H, 4.65; N, 12.91. Found: C, 77.52; H, 4.67; N,
13.13. δH (500 MHz, CDCl3) 8.30 (2H, d, J 8.6), 8.17 (2H, d, J 7.7), 7.77
(2H, d, J 8.6), 7.54ꢀ7.43 (4H, m), 7.34 (2H, t, J 7.4), 2.70 (3H, s). δC (126
MHz, CDCl3) 164.6, 164.2, 141.0, 140.5, 128.6, 127.5, 126.5, 124.0, 122.8,
120.8, 120.7, 109.9, 11.5. MS (EI): m/z 325.0 (M+, 100%). Crystals for
X-ray analysis were grown by slowly cooling a solution of 7a in MeCN.
2-[4-(2,7-Dimethoxy-9H-carbazol-9-yl)phenyl]-5-methyl-1,3,4-oxadiazole
(7b). Following the procedure for 7a, 6 (0.24 g, 1.4 mmol), 2,7-
dimethoxycarbazole (0.30 g, 1.4 mmol), K2CO3 (800 mg), and DMSO
(40 mL) gave 7b (0.36 g, 73%) as colorless crystals. Mp: 226.9ꢀ
228.3 °C. Anal. Calcd for C23H19N3O3: C, 71.67; H, 4.97; N, 10.90.
Found: C, 71.27; H, 4.96; N, 10.81. δH (700 MHz, CDCl3) 8.27 (2H, d,
J 8.5), 7.89 (2H, d, J 8.4), 7.72 (2H, d, J 8.5), 6.91ꢀ6.86 (4H, m), 3.83
(6H, s), 2.67 (3H, s). δC (176 MHz, CDCl3) 164.3, 163.8, 158.4, 141.7,
140.7, 128.5, 127.2, 122.7, 120.3, 117.7, 108.6, 94.4, 55.7, 11.2. MS (EI):
m/z 385.0 (M+, 100%).
cyclic voltammograms, and computational details. This material
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: m.r.bryce@durham.ac.uk; a.p.monkman@durham.ac.uk.
’ ACKNOWLEDGMENT
We thank the EPSRC for funding and John Dickinson for
assistance with obtaining some of the photophysical data.
’ REFERENCES
(1) Albinsson, B.; Eng, M. P.; Pettersson, K.; Winters, M. U. Phys.
Chem. Chem. Phys. 2007, 9, 5847–5864.
(2) Fukuzumi, S.; Guldi, D. M. In Electron Transfer in Chemistry;
Balzani, V., Ed.; Wiley-VCH: Weinheim, Germany; Vol. 2, pp 270ꢀ337.
(3) Adams, D. M.; Brus, L.; Chidsey, C. E. D.; Greager, S.; Creutz,
C.; Kagan, C. R.; Kamat, P. V.; Lieberman, M.; Lindsay, S.; Marcus, R. A.;
Metzger, R. M.; Michel-Beyerle, M. E.; Miller, J. R.; Newton, M. D.;
Rolison, D. R.; Sankey, O.; Schanze, K. S.; Yardley, J.; Zhu, X. J. Phys.
Chem. B 2003, 107, 6668–6697.
(4) Andrew, T. L.; Swager, T. M. J. Polym. Sci., Part B: Polym. Phys.
2011, 49, 476–498.
(5) Special Issue: π-Functional Materials. Chem. Mater. 2011, 23,
309ꢀ922.
(6) Maruccio, G.; R. Cingolani, R.; Rinaldi, R. J. Mater. Chem. 2004,
14, 542–554.
(7) Troisi, A.; Ratner, M. A. Small 2006, 2, 172–181.
(8) Special Issue: Organic Electronics. Chem. Mater. 2004, 16,
4381ꢀ4846.
(9) Special Issue: Organic Electronics and Optoelectronics. Chem.
Rev. 2007, 107, 923ꢀ1386.
(10) Gust, D.; Moore, T. A.; Moore, A. L. Acc. Chem. Res. 2001, 34,
40–48.
(11) Organic Light-Emitting Devices; M€ullen, K., Scherf, U., Eds.;
Wiley-VCH: Weinheim, 2006.
(12) Review: Laquai, F.; Park, Y.-S.; Kim, J.-J.; Baschꢀe, T. Macromol.
Rapid Commun. 2009, 30, 1203–1231.
(13) Sun, Y.; Giebink, N. C.; Kanno, H.; Ma, B.; Thompson, M. E.;
Forrest, S. R. Nature 2006, 440, 908–912.
(14) Grimsdale, A. C.; Chan, K. L.; Martin, R. E.; Jokisz, P. G.;
Holmes, A. B. Chem. Rev. 2009, 109, 897–1091.
(15) Shirota, Y.; Kageyama, H. Chem. Rev. 2007, 107, 953–1010.
(16) Delgado, J. L.; Bouit, P.-A.; Filippone, S.; Herranz, M. A.;
Martín, N. Chem. Commun. 2010, 46, 4853–4865.
(17) Giacalone, F.; Segura, J. L.; Martín, N.; Ramey, J.; Guldi, D. M.
Chem.—Eur. J. 2005, 11, 4819–4834.
(18) Thompson, A. L.; Ahn, T.-S.; Thomas, K. R. J.; Thayumanavan, S.;
Martínez, T. J.; Bardeen, C. J. J. Am. Chem. Soc. 2005, 127, 16348–16349.
(19) Adhikari, R. M.; Mondal, R.; Shah, B. K.; Neckers, D. C. J. Org.
Chem. 2007, 72, 4727–4732.
(20) Su, S.-J.; Sasabe, H.; Takeda, Kido, J. Chem. Mater. 2008,
20, 1691–1693.
(21) Tao, Y.; Wang, Q.; Yang, C.; Zhong, C.; Zhang, K.; Qin, J.; Ma,
D. Adv. Funct. Mater. 2010, 20, 304–311.
(22) Tokito, S.; Iijima, T.; Suzuri, Y.; Kita, H.; Tsuzuki, T.; Sato, F.
Appl. Phys. Lett. 2003, 83, 569–571.
Crystal Structure Determinations. Single-crystal X-ray diffrac-
tion experiments (Table 3) were carried out using graphite-monochro-
mated Mo Kα radiation (λ = 0.71073 Å) and open-flow N2 cryostats.
The structures were solved by direct methods and refined by full-matrix
least-squares on F2 of all data, using SHELXTL 6.1467 and OLEX2
software.68 Non-hydrogen atoms were refined with anisotropic displa-
cement parameters, methyl groups as rigid bodies, and other H atoms as
“riding” in idealized positions. In 5c, the tri(isopropyl)phenyl fragment
shows disorder which was resolved for four carbon atoms of the ring and
two of the 4-isopropyl group, which were refined in two positions each
with occupancies of 0.8 (anisotropic) and 0.2 (isotropic). Full crystal-
lographic data, excluding structure factors, have been deposited at the
Cambridge Crystallographic Data Center.
(23) Hanss, D.; Wenger, O. S. Eur. J. Inorg. Chem. 2009, 3778–3790.
(24) Schr€ogel, P.; Tomkeviꢁciene_, A.; Strohriegl, P.; Hoffmann, S. T.;
K€ohler, A.; Lennartz, C. J. Mater. Chem. 2011, 21, 2266–2273.
(25) Kamtekar, K. T.; Wang, C.; Bettington, S.; Batsanov, A. S.;
Perepichka, I. F.; Bryce, M. R.; Ahn, J. H.; Rabinal, M.; Petty, M. C.
J. Mater. Chem. 2006, 16, 3823–3835.
’ ASSOCIATED CONTENT
S
Supporting Information. X-ray crystal structures, NMR
b
spectra, absorption and emission spectra, fluorescence decays,
8309
dx.doi.org/10.1021/jo201488v |J. Org. Chem. 2011, 76, 8300–8310