85464-88-6Relevant articles and documents
Red or near-infrared light operating negative photochromism of a binaphthyl-bridged imidazole dimer
Kometani, Aya,Inagaki, Yuki,Mutoh, Katsuya,Abe, Jiro
, p. 7995 - 8005 (2020/05/27)
The development of red or near-infrared light (NIR) switchable photochromic molecules is required for an efficient utilization of sunlight and regulation of biological activities. While the photosensitization of photochromic molecules to red or NIR light has been achieved by a two-photon absorption process, the development of a molecule itself having sensitivity to red or NIR light has been now a challenging study. Herein, we developed an efficient molecular design for realizing red or NIR-light-responsive negative photochromism based on binaphthyl-bridged imidazole dimers. The introduction of electron-donating substituents shows the red shift of the absorption band at the visible-light region because of the contribution of a charge-transfer transition. Especially, the introduction of a di(4-methoxyphenyl)amino group (TPAOMe) and a perylenyl group largely shifts the absorption edge of the stable colored form to 900 nm. In addition, because the absorption band of one of the derivatives substituted with TPAOMe covers the whole visible-light region, the colored form shows a neutral gray color. Upon red (660 nm) or NIR-light (790 nm) irradiation, we observed the negative photochromic reaction from the stable colored form to the metastable colorless form. Therefore, the substituted binaphthyl-bridged imidazole dimers constitute the attractive photoswitches within a biological window.
Design and synthesis of new stable fluorenyl-based radicals
Tian, Yi,Uchida, Kazuyuki,Kurata, Hiroyuki,Hirao, Yasukazu,Nishiuchi, Tomohiko,Kubo, Takashi
, p. 12784 - 12793 (2015/02/19)
Organic neutral radicals have long fascinated chemists with a fundamental understanding of structure-reactivity relationships in organic reactions and with applications as new functional materials. However, the elusive nature of these radicals makes the synthesis, isolation, and characterization very challenging. In this work, the synthesis of three long-lived, fluorenyl-based radicals are reported. The geometry and electronic structures of these radicals were systematically investigated with a combination of various experimental methods, besides density functional theory (DFT) calculations, which include X-ray crystallographic analysis, electron spin resonance (ESR), electron nuclear double resonance (ENDOR), cyclic voltammetry, and UV-vis-NIR measurements. Their half-life periods (τ1/2) in air-saturated solution under ambient conditions were also determined. Surprisingly, all three radicals showed remarkable stabilities: τ1/2 = 7, 3.5, and 43 days.
Synthesis of axially chiral amino acid derivatives via the selective monoesterification of 1,1′-biaryl-2,2′-dicarboxylic acids
Furuta, Takumi,Nikaido, Masanori,Yamamoto, Junya,Kuribayashi, Toshifumi,Kawabata, Takeo
, p. 1312 - 1318 (2013/07/05)
Axially chiral amino acid derivatives were synthesized via a selective single-step monoesterification of 1,1′-binaphthyl-2,2′-dicarboxylic acids. In the presence of Ag2CO3, the alkylative monoesterification of a 1,1′-binaphthyl-2,2′-dicarboxylic acid with an alkyl halide proceeded selectively in a single operation. Curtius rearrangement of the monomethyl ester and successive alcoholysis of the corresponding isocyanate afforded the N-protected binaphthyl amino acids. Georg Thieme Verlag Stuttgart, New York.
