The Journal of Physical Chemistry B
ARTICLE
1
Data for 6b (n = 9): Yield 75%. H NMR (CDCl3): 0.67
’ ACKNOWLEDGMENT
(s, 3H), 0.84ꢀ2.04 (m, 38H), 2.38 (m, 2H), 3.40 (t, 2H, J = 7.0
Hz), 4.11 (t, 2H, J = 6.6 Hz), 4.46 (m, 1H), 5.40 (s, 1H).
13C NMR (CDCl3): 11.3, 18.2, 18.7, 20.5, 22.0, 22.3, 23.4, 23.7,
25.2, 27.2, 27.5, 27.6, 27.7, 28.1, 28.6, 28.7, 31.3, 32.3, 33.4, 35.2,
35.6, 36.0, 36.3, 37.5, 39.0, 39.2, 41.8, 49.5, 55.6, 56.1, 67.3, 122.3,
138.9, 154.1.
This work is partially supported by the Department of Energy
(DOE DE-SC0001412), the Air Force Office of Scientific
Research (AFOSR FA9550-09-1-0254), and the National Science
Foundation (NSF IIP 0750379). We thank Dr. A. Gericke for the
use of his characterization equipment.
1
Data for 6c (n = 11): Yield 81%. H NMR (CDCl3): 0.67
’ REFERENCES
(s, 3H), 0.84ꢀ2.04 (m, 38H), 2.41 (m, 2H), 3.41 (t, 2H, J = 6.8
Hz), 4.10 (t, 2H, J = 6.8 Hz), 4.40 (m, 1H), 5.40 (s, 1H). 13C NMR
(CDCl3): 11.8 18.7 19.2, 21.0, 22.5, 22.8, 23.8, 24.2, 25.7, 27.7,
28.0, 28.1, 28.6, 28.7, 29.2, 29.4, 31.8, 32.8, 34.0, 35.7, 36.1, 36.5,
36.8, 38.0, 39.5, 39.7, 42.3, 49.9, 56.1, 56.6, 67.8, 122.8, 139.3, 154.6.
Target Compounds 7aꢀc. A mixture of 5 (0.11 g, 0.25 mmol)
and potassium carbonate (0.10 g, 0.65 mmol) in anhydrous
acetone (20 mL) was stirred for 10 min and was refluxed slowly.
The solution of bromoalkyl cholesteryl ester 6 (0.55 mmol) in
acetone was added dropwise to the above reaction mixture. The
reaction was monitored by TLC. After completion, it was
extracted with dichloromethane (40 mL), washed with water
(50 mL), dried over sodium sulfate, and filtered and the solvent
was evaporated under reduced pressure. The residue was purified
by flash column chromatography with 10% ethyl acetate in
hexane to obtain the white powders which were recrystallized
twice with methylene chlorideꢀethanol to afford the target
compound 7.
(1) (a) Photochromism: Molecules and Systems; D€urr, H, Bouas-
Laurent, H., Eds.; Elsevier: Amsterdam, The Netherlands, 1990. (b)
Molecular Switches; Feringa, B. L., Ed.; Wiley-VCH: Weinheim, Germany,
2001. (c) Lemieux, V.; Gauthier, S.; Branda, N. R. Angew. Chem., Int. Ed.
2006, 45, 6820–6824. (d) Dulic, D.; Kudernac, T.; Puzys, A.; Feringa,
B. L.; Van Wees, B. J. Adv. Mater. 2007, 19, 2898–2902. (e) Jin, L.; Li, Y.;
Ma, J.; Li, Q. Org. Lett. 2010, 12, 3552–3555.
(2) (a) Irie, M. Chem. Rev. 2000, 100, 1685–1716. (b) Irie, M.;
Kobatake, S.; Horichi, M. Science 2001, 291, 1769–1772. (c) Shibata,
K.; Muto, K.; Kobatake, S.; Irie, M. J. Phys. Chem. A 2002,
106, 209–214. (d) Tian, H.; Yang, S. Chem. Soc. Rev. 2004,
33, 85–97. (e) Higashiguchi, K.; Matsuda, K.; Tanifuji, N.; Irie, M. J.
Am. Chem. Soc. 2005, 127, 8922–8923. (f) Tian, H.; Wang, S. Chem.
Commun. 2007, 781–792.
(3) (a) Leimieux, V.; Spantulescu, M. D.; Baldridge, K. K.; Branda,
N. R. Angew. Chem., Int. Ed. 2008, 47, 5034–5037. (b) Zhu, Y.; Yi, T.; Xiao,
S.; Li, F.; Li, C.; Gao, X.; Wu, J.; Yu, M.; Huang, C. J. Am. Chem. Soc. 2008,
130, 15750–15751. (c) Jiang, G.; Wang, S.; Yuan, W.; Jiang, L.; Song, Y.;
Tian, H.; Zhu, D. Chem. Mater. 2006, 18, 2335–2337. (d) Hayasaka, H.;
Tamura, K.; Akagi, K. Macromolecules 2008, 41, 2341–2346.
(4) (a) Li, Q.; Green, L.; Venkataraman, N.; Shiyanovskaya, I.; Asad,
Khan.; Urbas, A.; Doane, J .W. J. Am. Chem. Soc. 2007, 129, 12908–12909.
(b) Ma, J.; Li, Y.; White, T.; Urbas, A.; Li, Q. Chem. Commun. 2010,
46, 3463–3465. (c) Mathews, M.; Zola, R. S.; Hurley, S.; Yang, D. K.;
White, T. J.; Bunning, T. J.; Li, Q. J. Am. Chem. Soc. 2010,
132, 18361–18366. (d) Mathews, M.; Zola, R. S.; Yang, D. K.; Li., Q. J.
Mater. Chem. 2011, 21, 2098–2103.
Data for 7a (n = 6): 1H NMR (CDCl3): 0.55ꢀ1.93 (m, 72H),
2.29 (d, 4H, J = 7.9 Hz), 2.83 (t, 4H, J = 7.0 Hz), 3.95 (t, 4H, J =
6.19 Hz), 4.13 (t, 4H, J = 6.6 Hz), 4.37 (m, 2H), 5.4 (s, 2H), 6.82
(t, 6H, J = 8.4 Hz), 7.38 (d, 4H, J = 8.6 Hz). 13C NMR (CDCl3):
11.8, 14.36, 18.72, 19.27, 21.0, 22.5, 22.8, 23.8, 24.2, 25.5, 25.7,
27.7, 28.0, 28.2, 28.6, 29.1, 31.8, 35.7, 36.1, 36.5, 36.8, 38.0, 38.4,
39.5, 39.7, 42.3, 49.9, 56.1, 56.6, 67.6, 67.8, 114.7, 122.8, 126.5,
127.3, 133.3, 134.4, 136.4, 139.3, 139.4, 154.6, 158.2. Anal. Calcd
for C96H140O8S2: C, 77.30; H, 9.22; S, 4.12. Found: C, 77.58; H,
9.49; S, 4.31.
(5) (a) Denekamp, C.; Feringa, B. L. Adv. Mater. 1998,
10, 1080–1082. (b) Uchida, K.; Kawai, Y.; Shimizu, Y.; Vill, V.; Irie,
M. Chem. Lett. 2000, 6, 654–655.
Data for 7b (n = 9): 1H NMR (CDCl3): 0.68ꢀ2.10 (m, 99H),
2.41 (d, 4H, J = 6.0 Hz), 2.83 (t, 4H, J = 8.0 Hz), 3.95 (d, 4H,
J = 6.0 Hz), 4.12 (t, 4H, J = 6.4 Hz)), 4.47 (m, 2H), 5.40 (s, 2H),
6.88 (t, 6H, J = 7.4 Hz), 7.42 (d, 4H, J = 8.0 Hz). 13C NMR
(CDCl3): 11.8, 14.36, 18.71, 19.27, 21.0, 22.5, 22.8, 23.8, 24.2,
25.7, 26.0, 27.7, 28.0, 28.2, 28.6, 29.1, 29.2, 29.3, 31.8, 35.7, 36.1,
36.5, 36.8, 38.0, 38.4, 39.5, 39.7, 42.3, 49.9, 56.1, 56.6, 67.8, 68.0,
114.7, 122.8, 126.4, 127.2, 133.3, 134.4, 136.4, 139.3, 139.5,
154.6, 158.3. Anal. Calcd for C102H152O8S2: C, 77.79; H, 9.68; S,
4.02. Found: C, 78.01; H, 9.76; S, 4.08.
(6) (a) Chen, S. H.; Chen, H. M. P.; Geng, Y.; Jacobs, S. D.; Marshall,
K. L.; Blanton, T. N. Adv. Mater. 2003, 15, 1061–1065. (b) Frigoli, M.;
Welch, C.; Mehl, G. H. J. Am. Chem. Soc. 2004, 126, 15382–15383. (c)
Frigoli, M. L.; Mehl, G. H. Chem.—Eur. J. 2004, 10, 5243–5250. (d)
Frigoli, M.; Mehl, G. H. Chem. Commun. 2004, 818–819. (e) Frigoli, M.;
Mehl, G. H. Chem. Commun. 2004, 2040–2041. (f) Subramanian, G.;
Lehn, J. M. Mol. Cryst. Liq. Cryst. 2001, 364, 423–251.
(7) Kim, C.; Marshall, K. L.; Wallace, J. U.; Chen, S. H. J. Mater.
Chem. 2008, 18, 5592–5598.
(8) (a) Green, L.; Li, Y.; White, T.; Urbas, A.; Bunning, T.; Li, Q.
Org. Biomol. Chem. 2009, 7, 3930–3933. (b) Yelamaggad, C. V.;
Shashikala, I. S.; Li, Q. Chem. Mater. 2007, 19, 6561–6568.
(9) (a) Wang, S.; Shen, W.; Feng, Y.; Tian, H. Chem. Commun.
2006, 1497–1499. (b) Liu, B; Tian, H. J. Mater. Chem. 2005,
15, 2681–2686. (c) Tian, H.; Feng, Y. J. Mater. Chem. 2008,
18, 1617–1622. (d) Li, Y.; Cao, L.; Tian, H. J. Org. Chem. 2006,
71, 8279–8282.
Data for 7c (n = 11): 1H NMR (CDCl3): 0.66ꢀ2.02
(m, 123H), 2.41 (d, 4H, J = 6.0 Hz), 2.82 (t, 4H, J = 8.0 Hz), 3.97
(d, 4H, J = 6.0 Hz), 4.12 (t, 4H, J = 6.4 Hz), 4.46 (m, 2H), 5.39
(s, 2H), 6.87 (t, 6H, J = 7.4 Hz), 7.42 (d, 4H, J = 8.0 Hz). 13C
NMR (CDCl3): 11.8, 14.36, 18.71, 19.2, 21.0, 22.56, 22.82,
24.28, 25.7, 26.0, 27.7, 28.0, 28.2, 28.6, 29.2, 29.3, 29.4, 31.84,
35.7, 36.1, 36.5, 36.8, 38.0, 38.4, 39.5, 39.7, 42.3, 49.9, 56.1, 67.8,
68.0, 114.7, 122.8, 126.4, 122.2, 133.2, 134.4, 136.4, 139.3, 139.5,
154.6, 158.3. Anal. Calcd for C106H160O8S2: C, 78.12; H, 9.81; S,
3.90. Found: C, 78.27; H, 9.91; S, 3.94.
(10) Dierking, I. Textures of Liquid Crystals; Wiley-VCH GmBH &
KGaA: Weinheim, Germany, 2003.
(11) (a) Chen, S. H.; Shi, H.; Conger, B. M.; Mastrangelo, J. C.;
Tsutsui, T. Adv. Mater. 1996, 8, 998–1001. (b) Chen, S. H.; Katsis, D.;
Mastrangelo, J. C.; Schmid, A. W.; Tsutsui, T.; Blanton, T. N. Nature
1999, 397, 506–508. (c) Chen, H. P.; Katsis, D.; Mastrangelo, J. C.;
Chen, S. H.; Jacobs, S. D.; Hood, P. J. Adv. Mater. 2000, 12, 1283–1286.
(d) Philip, H. M.; Katsis, D.; Chen, S. H. Chem. Mater. 2003,
15, 2534–2542.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: qli1@kent.edu. Phone: 330-672-1537. Fax: 330-672-
2796.
(12) Li, Q.; Li, L.; Kim, J.; Park, H.-S.; Williams, J. Chem. Mater.
2005, 17, 6018–6021.
3414
dx.doi.org/10.1021/jp112401k |J. Phys. Chem. B 2011, 115, 3409–3415