期刊
CRYSTAL GROWTH & DESIGN
卷 19, 期 2, 页码 1384-1390出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.cgd.8b01764
关键词
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资金
- Nanotechnology Platform of the Ministry of Education, Culture, Sports, Science and Technology (MEXT) of Japan
- Japan Society for the Promotion of Science [16K05743, 17H06367]
- Grants-in-Aid for Scientific Research [16K05743] Funding Source: KAKEN
Single-crystal microscopic absorption spectroscopy was used to clarify the effect of a bulky substituent on the photochromic properties of salicylideneanilines. We discovered that 3,5-di-tert-butylsalicylideneaniline (1), exhibiting debatable chromic properties, had at least three crystalline polymorphs, alpha(1), alpha(1), and beta. alpha(1)-1 is thermochromic from -75 to 45 degrees C and also photochromic, particularly from -75 to 0 degrees C; alpha(2)-1 is photochromic but considerably unstable and transforms into the beta form; beta-1 is thermochromic from -75 to 90 degrees C but not photochromic. The 4'-methyl analogue of 1 (2) is simultaneously thermochromic and photochromic, especially around 75 degrees C, and the 4'-chloro analogue (3) is thermochromic from -75 to 90 degrees C and is more strongly photochromic at lower temperatures. Comparison of the crystal structures facilitated the identification of some common features among the photochromic species. We demonstrated a quantitative temperature-dependent photochromic response profile for the first time. The observed temperature dependence of photoinduced spectral changes presents an intrinsic challenge to the conventional dualistic classification of compounds as photo- or thermochromic.
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