Journal of the American Chemical Society
Communication
(19) Note that in the parent azobenzene photoswitching upon n→π*
excitation is possible due to the fact that the Z-isomer exhibits a higher
molar absorption coefficient than the E-isomer.
and hence the amplitude of the photoinduced motion/
actuation.
(20) Hoffmann, R. Acc. Chem. Res. 1971, 4, 1.
(21) Hammett, L. P. J. Am. Chem. Soc. 1937, 59, 96.
(22) See Supporting Information.
ASSOCIATED CONTENT
* Supporting Information
Experimental details including synthesis, photochemistry, and
computational methods. This material is available free of charge
■
S
(23) The calculations indicate that the energy surface for twisting
about the CC−NN bonds is shallow up to ∼30°; see Figure S7.
(24) All PSS compositions were determined by ultraperformance
liquid chromatography (UPLC) analyses using integration of the UV
signal at the wavelengths of the isosbestic points.
(25) Note that in the covalently bridged azobenzene the Z form is
thermodynamically favored over the E-isomer as a result of the ring
strain.
(26) Note that calculations performed at the G3MP2 level of theory
give an energy difference between the E and Z isomers in better
agreement with the experimental value of 11.4 kcal/mol previously
determined: Cammenga, H. K.; Emel’yanenko, V. N.; Verevkin, S. P.
Ind. Eng. Chem. Res. 2009, 48, 10120.
(27) Samanta, S.; Qin, C.; Lough, A. J.; Woolley, A; G. Angew. Chem.,
Int. Ed. 2012, 51, 6452.
(28) (a) Park, J.; Yuan, D. Q.; Pham, K. T.; Li, J. R.; Yakovenko, A.;
Zhou, H. C. J. Am. Chem. Soc. 2012, 134, 99. (b) Yanai, N.; Uemura,
T.; Inoue, M.; Matsuda, R.; Fukushima, T.; Tsujimoto, M.; Isoda, S.;
Kitagawa, S. J. Am. Chem. Soc. 2012, 134, 4501.
AUTHOR INFORMATION
Corresponding Author
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
Generous support by the German Research Foundation (DFG
via SFB 658, project B8) is gratefully acknowledged. BASF AG,
Bayer Industry Services, and Sasol Germany are thanked for
generous donations of chemicals.
(29) The molar absorption coefficient of azobenzenes 1 and 3 is
∼20 000 M−1 cm−1 for the π→π* transition vs ∼1000 M−1 cm−1 for
the n→π* transition.
REFERENCES
■
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(17) Note that the spectral properties of azobenzene derivatives
ortho-functionalized with fluorine atoms were already described, but no
separation of the n→π* bands was reported: (a) Ishikawa, N.;
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(18) See Supporting Information (p S14) for a more detailed
comparison of the effects of ortho-fluorine atoms and ortho-methoxy
groups on the energetic levels of azobenzene.
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dx.doi.org/10.1021/ja310323y | J. Am. Chem. Soc. XXXX, XXX, XXX−XXX