Highly efficient reversible Z-E photoisomerization of a bridged azobenzene with visible light through resolved S(1)(n pi*) absorption bands

J Am Chem Soc. 2009 Nov 4;131(43):15594-5. doi: 10.1021/ja906547d.


The reversible Z-E photoswitching properties of the (Z) and (E) isomers of the severely constrained bridged azobenzene derivative 5,6-dihydrodibenzo[c,g][1,2]diazocine (1) were investigated quantitatively by UV/vis absorption spectroscopy in solution in n-hexane. In contrast to normal azobenzene (AB), 1 has well separated S(1)(n pi*) absorption bands, peaking at lambda(Z) = 404 nm and lambda(E) = 490 nm. Using light at lambda = 385 nm, it was found that 1Z can be switched to 1E with very high efficiency, Gamma = 92 +/- 3%. Conversely, 1E can be switched back to 1Z using light at lambda = 520 nm with approximately 100% yield. The measured quantum yields are Phi(Z-->E) = 72 +/- 4% and Phi(E-->Z) = 50 +/- 10%. The thermal lifetime of the (E) isomer is 4.5 +/- 0.1 h at 28.5 degrees C. The observed photochromic and photoswitching properties of 1 are much more favorable than those for normal AB, making our title compound a promising candidate for interesting applications as a molecular photoswitch especially at low temperatures. The severe constraints by the ethylenic bridge apparently do not hinder but favor the Z-E photoisomerization reactions.