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DOI: 10.1039/A806802J (Paper) Reference Section for: J. Mater. Chem., 1998, 8, 2579-2581

4-[Di(biphenyl-4-yl)amino]azobenzene and 4,4′-bis[bis(4′-tert-butylbiphenyl-4-yl)amino]azobenzene as a novel family of photochromic amorphous molecular materials

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Yasuhiko Shirota, Kazuyuki Moriwaki, Satoru Yoshikawa, Toshiki Ujike and Hideyuki Nakano

Abstract

We have created photochromic amorphous molecular materials containing an azobenzene chromophore, 4-[di(biphenyl-4-yl)amino]azobenzene and 4,4′-bis[bis(4′-tert-butylbiphenyl-4-yl)amino]azobenzene (t-BuBBAB), which readily form amorphous glasses above room temperature and exhibit photochromism in their amorphous films. We have shown that the photogenerated cis-form in the amorphous film can be stabilized at ambient temperature by the incorporation of a bulky group; the backward cis→trans thermal isomerization can be controlled by temperature for t-BuBBAB.

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  11. DBAB: Yield 45%. Mp 223 °C; δH(600 MHz, THF-d8, TMS) 7.20 (d, 2H), 7.27 (d, 4H), 7.28 (t, 2H), 7.40 (t, 4H), 7.41 (t, 1H), 7.47 (t, 2H), 7.63 (d, 8H), 7.84 (d, 2H), 7.86 (d, 2H)m/z(EI) 501 (M+); Calc. for C36H27N3: C, 86.20; H, 5.42; N, 8.38. Found: C, 86.04; H, 5.41; N, 8.23%; λmax(toluene)(log ε) for trans-DBAB: 335 nm (4.5), 435 nm (4.5); λmax(toluene)(log ε) for cis-DBAB: 343 nm (4.5), 451 nm (3.9); t-BuBBAB: Yield 21%. Mp 356 °C; δH(600 MHz, 1,4-dioxane-d8, TMS) 1.34 (s, 36H), 7.23 (d, 4H), 7.28 (d, 8H), 7.46 (d, 8H), 7.54 (d, 8H), 7.57 (d, 8H), 7.80 (d, 4H); m/z(EI) 1044 (M+); Calc. for C76H76N4: C, 87.31; H, 7.33; N, 5.36. Found: C, 87.11; H, 7.24; N, 5.35%; λmax(toluene)(log ε) for trans-t-BuBBAB: 345 nm (4.7), 480 nm (4.7); λmax(toluene)(log ε) for cis-t-BuBBAB: 342 nm (4.8), 488 nm (3.9).
  12. The cis→trans thermal isomerization in the amorphous film could be analyzed in terms of the first-order kinetics consisting of two components. The rate constants for the faster component with a fraction of 0.05 and slower one with a fraction of 0.95 were 0.12 min–1 and 3.3 × 10–3 min–1, respectively.
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