DOI: 10.1039/C4NJ01653J
New Journal of Chemistry
ARTICLE
Journal Name
in anhydrous THF (10 mL) was dropwise added solution of purified by silica chromatography to give C2 as a blue solid in
compound 5b (0.6 g, 1.4 mmol) in anhydrous THF at 0 ºC 67.9 % yield (0.19 g, 0.3 mmol). m.p. : 143.87 ºC . MS, m/z:
+
1
under N circumstance, then the solution heated up to 70 ºC for 633.109 (M ), H NMR (400 MHz, Acetone) δ 8.14 (dd, J =
2
3
h. After the reaction completed, poured the solution into 15.1, 12.0 Hz, 1H), 7.84 – 7.71 (m, 3H), 7.69 – 7.63 (m, 1H),
saturated ammonium chloride solution. The organic phase was 7.62 – 7.56 (m, 1H), 7.48 – 7.44 (m, 1H), 7.38 – 7.31 (m, 2H),
extracted by AcOEt, washed with brine and dried over MgSO4. 7.28 – 7.17 (m, 1H), 7.11 (d, J = 16.1 Hz, 1H), 6.65 (dd, J =
After removal of the solvent under reduced pressure, the crude 23.0, 9.1 Hz, 2H), 2.51 (dd, J = 36.2, 29.0 Hz, 4H), 2.08 (ddd, J
product was purified by silica chromatography to give 6b as a = 6.3, 5.7, 2.2 Hz, 4H), 1.82 (d, J = 15.3 Hz, 6H), 1.11 – 0.92
1
3
yellow oil in 87.3 % yield (0.55 g, 1.2 mmol). MS, m/z: (m, 10H), 0.70 – 0.45 (m, 10H). C NMR (100 MHz, CDCl ) δ
3
+
1
4
3
7
49.587 (M ), H NMR (400 MHz, Acetone) δ 7.64 (ddd, J = 175.89, 173.29, 154.05, 151.57, 151.23, 146.97, 143.67, 142.39,
0.4, 17.1, 10.7 Hz, 3H), 7.45 (ddd, J = 14.7, 7.9, 1.2 Hz, 1H), 140.57, 135.59, 134.06, 133.69, 131.15, 129.82, 128.39, 127.58,
.31 (dd, J = 8.0, 4.6 Hz, 1H), 7.24 – 7.17 (m, 2H), 7.17 – 6.90 127.00, 126.38, 123.01, 121.40, 120.12, 119.97, 116.36, 112.24,
(
m, 2H), 6.55 (dd, J = 71.5, 42.1 Hz, 1H), 5.33 – 5.03 (m, 1H), 111.58, 111.39, 96.89, 95.52, 55.03, 40.27, 39.97, 39.61, 31.43,
2
0
.38 – 2.17 (m, 4H), 2.05 – 1.93 (m, 4H), 1.09 – 0.77 (m, 10H), 28.49, 28.29, 26.45, 26.04, 23.08, 13.77. Anal. Calcd. for
.77 – 0.37 (m, 10H). C H N O (%): C, 83.37; H, 7.47; N, 6.63. Found: C, 83.39; H,
Compound 7b. A solution of compound 6b (0.55 g, 1.2 7.41; N, 6.70.
4
4
47
3
mmol) in anhydrous toluene (10 mL) was prepared in a three
neck flask which was purged with nitrogen, then the solution Acknowledgements
was cooled to -78 ºC and dropwise added DIBAH (2.5 mL),
We are grateful to the National Natural Science Foundation of
China (No. 1110 4284 and No. 61101054) for the financial
support.
after this, the resulting mixture was stirred for 2 h. Wet silica-
gel powder was added to the solution to quench the reaction,
then the temperature rose to 0 ºC and reacted for 1 h. The
organic phase was extracted by AcOEt, washed with brine and
Notes and references
dried over MgSO . After removal of the solvent under reduced
4
a
Key Laboratory of Photochemical Conversion and Optoelectronic
pressure, the crude product was purified by silica
Materials, Technical Institute of Physics and Chemistry, Chinese
chromatography to give 7b as an orange oil in 72.2 % yield (0.4
+
1
g, 0.9 mmol, Z/E=1/0.59). MS, m/z: 452.322 (M ), H NMR
400 MHz, Acetone) δ 10.15 (d, J = 7.9 Hz, 1H), 9.99 (d, J =
(
8
b
2543528; Fax: +86-010-82543529.
8
7
–
1
.1 Hz, 0.59H), 7.70 – 7.63 (m, 3H), 7.59 (d, J = 2.0 Hz, 1.5H),
.45 (dd, J = 7.9, 1.4 Hz, 1.5H), 7.36 (d, J = 11.5 Hz, 1H), 7.35
7.28 (m, 1.6H), 7.25 – 7.17 (m, 3H), 7.09 (t, J = 17.5 Hz,
.7H), 6.94 (dd, J = 16.2, 9.6 Hz, 1.6H), 6.36 (s, 0.6H), 5.76 (d,
University of Chinese Academy of Sciences, Beijing 100043, PR China
†
Electronic Supplementary Information (ESI) available: TGA curves and
frontier orbitals composition for chromophores C1 and C2
.
J = 8.1 Hz, 0.67H), 5.58 (d, J = 7.8 Hz, 1H), 2.34 (d, J = 2.8 Hz,
1
F. Kajzar, K.-S. Lee and A. Y. Jen, in Polymers for Photonics
Applications II, ed. K.-S. Lee, Springer Berlin Heidelberg, 2003, 161,
pp. 1
3
0
H), 2.20 (t, J = 17.4 Hz, 2.5H), 2.09 – 1.94 (m, 6.4H), 1.02 –
.72 (m, 16H), 0.58 – 0.32 (m, 16H).
2
3
4
Z. Li, Q. Li and J. Qin, Polym Chem, 2011, 2, 2723.
W. Wu, R. Tang, Q. Li and Z. Li, Chem Soc Rev, 2014.
M. Hochberg, T. Baehr-Jones, G. Wang, M. Shearn, K. Harvard, J.
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and A. Scherer, Nat Mater, 2006, 5, 703.
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T. Ho and T. J. Marks, Angew Chem Int Ed, 2005, 44, 7922.
Chromophore C1. A solution of compound 6a (0.5 g, 1.2
mmol) and TCF acceptor (0.28 g, 1.4 mmol) in ethanol (20 mL)
was allowed to stir at 80 ºC for 12 h, then after removal of the
solvent under reduced pressure, the crude product was purified
by silica chromatography to give C1 as a purple solid in 41.2 %
yield (0.3 g, 0.5 mmol). m.p. : 169.22 ºC . MS, m/z: 595.733
5
+
1
(
7
(
3
(
(
M ), H NMR (400 MHz, Acetone) δ 8.04 (d, J = 16.0 Hz, 1H),
.70 (dd, J = 7.3, 4.4 Hz, 3H), 7.59 (d, J = 4.0 Hz, 1H), 7.51
dd, J = 18.1, 12.0 Hz, 2H), 7.37 – 7.28 (m, 2H), 7.27 – 7.18 (m,
H), 6.78 (d, J = 16.0 Hz, 1H), 2.02 – 1.94 (m, 4H), 1.86 – 1.70
6 T.-D. Kim, J.-W. Kang, J. Luo, S.-H. Jang, J.-W. Ka, N. Tucker, J. B.
Benedict, L. R. Dalton, T. Gray, R. M. Overney, D. H. Park, W. N.
Herman and A. K. Y. Jen, J Am Chem Soc, 2007, 129, 488.
7
J. Wu, S. Bo, J. Liu, T. Zhou, H. Xiao, L. Qiu, Z. Zhen and X. Liu,
Chem Commun, 2012, 48, 9637.
1
3
8 C. Zhang, L. R. Dalton, M.-C. Oh, H. Zhang and W. H. Steier, Chem
Mater, 2001, 13, 3043.
9
m, 6H), 1.03 – 0.88 (m, 4H), 0.58 – 0.34 (m, 10H). C NMR
100 MHz, Acetone) δ 175.68, 173.58, 150.75, 150.69, 150.44,
W. Gong, Q. Li, Z. Li, C. Lu, J. Zhu, S. Li, J. Yang, Y. Cui and J. Qin,
1
1
1
2
41.63, 140.07, 138.94, 138.51, 136.35, 134.88, 132.89, 127.83,
26.89, 126.37, 125.90, 122.35, 120.80, 119.86, 119.41, 119.29,
12.73, 111.52, 110.86, 109.98, 97.85, 97.63, 54.32, 39.21,
5.36, 24.70, 22.09, 12.49. Anal. Calcd. for C H N OS (%):
J Phys Chem B, 2006, 110, 10241.
0 Q. Li, C. Lu, J. Zhu, E. Fu, C. Zhong, S. Li, Y. Cui, J. Qin and Z. Li, J
Phys Chem B, 2008, 112, 4545.
1 L. R. Dalton, P. A. Sullivan and D. H. Bale, Chem Rev, 2009, 110, 25.
12 M. Lee, H. E. Katz, C. Erben, D. M. Gill, P. Gopalan, J. D. Heber and
D. J. McGee, Science, 2002, 298, 1401.
3 S. J. Benight, D. H. Bale, B. C. Olbricht and L. R. Dalton, J Mater
Chem, 2009, 19, 7466.
4 M. J. Cho, D. H. Choi, P. A. Sullivan, A. J. P. Akelaitis and L. R.
Dalton, Prog Polym Sci, 2008, 33, 1013.
1
1
3
9
37
3
C, 78.62; H, 6.26; N, 7.05. Found: C, 78.59; H, 6.25; N, 7.08.
Chromophore C2. A solution of compound 7b (0.2 g, 0.44
mmol) and TCF acceptor (0.11 g, 0.55 mmol) in ethanol (20
mL) was allowed to stir at 75 ºC for 12 h, then after removal of
the solvent under reduced pressure, the crude product was
1
1
1
5 D. R. Kanis, M. A. Ratner and T. J. Marks, Chem Rev, 1994, 94, 195.
6
| J. Name., 2012, 00, 1-3
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