Found: C, 54.80; H, 4.70; N, 2.30%. HRMS: m/z = 573.1069
[M]+ (calc. for C26H25F6N1S2Si = 573.1051).
reflections = 6585, independent reflections with I 4 2s(I) =
4381, R1 (all data) = 0.1086 and wR2 (all data) = 0.2618.w
Preparation of 1(o,o)
References
To a THF solution of 6 (350 mg, 0.64 mmol) and 7 (126 mg,
0.28 mmol) was added t-BuOK (77 mg, 0.70 mmol). After
refluxing overnight, the reaction mixture was hydrolyzed
with water, and the organic phase washed with a saturated
solution of Na2CO3, dried over MgSO4 and evaporated
in vacuo. The residue was recrystallized from a CH2Cl2/pentane
mixture at ꢂ20 1C to give 1(o,o) as a red powder (180 mg,
1 (a) M. Irie, Chem. Rev., 2000, 100, 1685; (b) H. Tian and S. Yang,
Chem. Soc. Rev., 2004, 33, 85; (c) F. M. Raymo and M. Tomasulo,
J. Phys. Chem. A, 2005, 109, 7343.
2 Selected examples: (a) Y.-C. Jeong, S. I. Yang, K.-H. Ahn and
E. Kim, Chem. Commun., 2005, 2503; (b) G. Jiang, S. Wang,
W. Yuan, L. Jiang, Y. Song, H. Tian and D. Zhu, Chem. Mater.,
2006, 18, 234; (c) M.-Q. Zhu, L. Zhu, J. J. Han, W. Wu, J. K. Hurst
and A. D. Q. Li, J. Am. Chem. Soc., 2006, 128, 4303; (d) S.-J. Lim,
J. Seo and S. Y. Park, J. Am. Chem. Soc., 2006, 128, 14542;
(e) Z. Zhou, S. Xiao, J. Xu, Z. Liu, M. Shi, F. Li, T. Yi and
C. Huang, Org. Lett., 2006, 8, 3911; (f) T. Fukaminato,
T. Umemoto, Y. Iwata, S. Yokojima, M. Yoneyama,
S. Nakamura and M. Irie, J. Am. Chem. Soc., 2007, 129, 5932;
(g) L. Zhu, W. Wu, M.-Q Zhu, J. J. Han, J. K. Hurst and A. D.
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D. Kozlov and D. C. Neckers, J. Org. Chem., 2005, 70, 5545.
3 Selected examples: (a) A. Fernandez-Acebes and J.-M. Lehn,
Chem.–Eur. J., 1999, 5, 3285; (b) V. W.-W. Yam, C.-C. Ko and
N. Zhu, J. Am. Chem. Soc., 2004, 126, 12734; (c) R. T. F. Jukes,
V. Adamo, F. Hartl, P. Belser and L. De Cola, Inorg. Chem., 2004,
43, 2779; (d) P. H.-M. Lee, C.-C. Ko, N. Zhu and V. W.-W. Yam,
J. Am. Chem. Soc., 2007, 129, 6058.
1
3
50%). H NMR (500 MHz, CDCl3): d 8.63 (d, J = 5.1 Hz,
3
1H, Py6), 8.26 (s, 1H, Py3), 7.53 (d, J = 8.9 Hz, 2H, C6H4),
7.25 (s, 1H, thio), 7.23 (s, 1H, thio), 7.17 (dd, 3J = 5.1 Hz and
4J = 1.6 Hz, 1H, Py5), 6.94 (d, 3J = 15.9 Hz, 1H,QCH), 6.77
(d, 3J = 8.9 Hz, 2H, C6H4), 6.71 (d, 3J = 15.9 Hz, 1H,QCH),
3.05 (s, 6H, NMe2), 1.99 (s, 3H, Me) and 0.03 (s, 9H, TMS).
13C[1H] NMR (125 MHz, CDCl3): d 156.4, 150.7, 149.4, 147.8,
147.5, 146.2, 144.7, 139.5, 138.5, 133.5, 128.4, 126.9, 126.5,
125.6, 123.5, 120.9, 120.7, 119.6, 119.0, 112.3, 40.3, 14.5 and
ꢂ0.6. Anal. calc. for C64H58F12N4S4Si2: C, 59.33; H, 4.51; N,
4.32. Found: C, 59.87; H, 4.86; N, 4.79%. HRMS: m/z =
1294.2875 [M]+ (calc. for C64H58F12N4Si2S4 = 1294.2891).
4 M. Giraud, A. Leaustic, R. Guillot, P. Yu, P. G. Lacroix,
´
K. Nakatani, R. Pansu and F. Maurel, J. Mater. Chem., 2007,
17, 4414.
5 (a) O. Maury, L. Viau, K. Senechal, B. Corre, J.-P. Guegan,
´ ´ ´
T. Renouard, I. Ledoux, J. Zyss and H. Le Bozec, Chem.–Eur.
J., 2004, 10, 4454; (b) O. Maury and H. Le Bozec, Acc. Chem. Res.,
2005, 38, 691.
6 V. Aubert, V. Guerchais, E. Ishow, K. Hoang-Thi, I. Ledoux,
K. Nakatani and H. Le Bozec, Angew. Chem., Int. Ed., 2008, 47,
577.
7 For examples of DTE derivatives substituted at the 2-positions of
the thiophene rings, see: (a) T. Kodani, K. Matsuda, T. Yamada,
S. Kobatake and M. Irie, J. Am. Chem. Soc., 2000, 122, 9631;
(b) N. Tanifuji, M. Irie and K. Matsuda, J. Am. Chem. Soc., 2005,
127, 13344; (c) A. Peters, R. McDonald and N. R. Branda, Chem.
Commun., 2002, 2274; (d) K. Yumoto, M. Irie and K. Matsuda,
Org. Lett., 2008, 10, 2051.
Spectroscopic characterization of 1(c,o)
Compound 1(c,o) was generated by the irradiation (l = 436 nm)
of a d12-cyclohexane solution of 1(o,o) for 30 min. Selected data:
1H NMR (500 MHz, d12-cyclohexane): d 8.48 and 8.46 (2 ꢁ d,
3J = 5 Hz, 2H, Py6), 8.49 and 8.42 (2 ꢁ s, 2H, Py3), 7.58 (d,
3J = 15.7 Hz, 1H, QCH(c)), 7.25 (s, 1H, thio(o)), 7.21 (s, 1H,
thio(o)), 7.09 and 6.95 (2 ꢁ dd, 3J = 5.1 Hz, 2H, Py5), 6.92 (d,
3J = 15.9 Hz, 1H, QCH(o)), 6.70 (s, 1H, thio(c)), 6.33 (s, 1H,
thio(c)), 2.97 and 2.96 (2 ꢁ s, 12 H, NMe2), and 2.04 and 1.96
(2 ꢁ s, 6H, Me).
X-Ray diffraction study of 1(o,o)
8 (a) T. Yamada, S. Kobatake, K. Muto and M. Irie, J. Am. Chem.
Soc., 2000, 122, 1589; (b) H. Choi, H. Lee, Y. Kang, E. Kim,
S. O. Kang and J. Ko, J. Org. Chem., 2005, 70, 8291.
´
9 O. Maury, J.-P. Guegan, T. Renouard, A. Hilton, P. Dupau,
N. Sandon, L. Toupet and H. Le Bozec, New J. Chem., 2001, 25,
1553.
10 For examples of multi-DTE-based systems with partial photo-
cyclization, see: (a) T. Kawai, T. Sasaki and M. Irie, Chem.
Commun., 2001, 711; (b) H. Tian, B. Chen, H. Tu and
Single crystals for X-ray diffraction studies were grown by the
slow evaporation of a CH2Cl2 solution of complex 1(o,o) at
20 1C. The sample (0.32 ꢁ 0.28 ꢁ 0.28 mm) was studied on an
Oxford Diffraction Xcalibur Saphir 3 diffractometer with
graphite monochromatized Mo-Ka radiation. C64H58F12N4S4Si2,
M
=
1295.6, monoclinic, P21/n,
a
=
10.45582(5),
100.277(4)1,
b
=
19.8097(9), 14.9154(7) A,
c
=
b
=
K. Mullen, Adv. Mater., 2002, 14, 918; (c) I. Jung, H. Choi,
¨
V = 3040.5(2) A3, Z = 2, rcalc = 1.415 g cmꢂ3, mMo-K
, reflections collected = 21731, independent
=
E. Kim, C.-H. Lee, S. O. Kang and J. Ko, Tetrahedron, 2005,
61, 12256.
a
2.77 mmꢂ1
ꢀc
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2009 New J. Chem., 2009, 33, 1320–1323 | 1323