Volume 21, Issue 18 p. 6747-6755
Full Paper

Photoinduced Formation of an Azobenzene-Based CD-Active Supramolecular Cyclic Dimer

Dr. Hiromitsu Sogawa

Dr. Hiromitsu Sogawa

Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura Campus, Nishikyo-ku, Kyoto 615-8510 (Japan)

Present Address: Department of Organic and Polymeric Materials, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152-8552 (Japan)

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Dr. Kayo Terada

Dr. Kayo Terada

Graduate School of Materials Science, Nara Institute of Science and Technology, Takayama-cho, Ikoma 630-0192 (Japan)

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Yu Miyagi

Yu Miyagi

Department of Chemistry and Materials Engineering, Faculty of Chemistry, Materials and Bioengineering, Kansai University, 3-3-35 Yamate-cho, Suita, Osaka 564-8680 (Japan)

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Prof. Dr. Masashi Shiotsuki

Prof. Dr. Masashi Shiotsuki

Faculty of Engineering, Tokyo City University, Tamadutsumi 1-28-1, Setagaya-ku, Tokyo 158-8557 (Japan)

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Prof. Dr. Yoshihito Inai

Prof. Dr. Yoshihito Inai

Department of Frontier Materials, Shikumi College, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555 (Japan)

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Prof. Dr. Toshio Masuda

Prof. Dr. Toshio Masuda

Department of Polymer Materials, School of Materials Science and Engineering, Shanghai University, Materials Building, Nanchen 333, Shanghai 200444 (P.R. China)

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Prof. Dr. Fumio Sanda

Corresponding Author

Prof. Dr. Fumio Sanda

Department of Chemistry and Materials Engineering, Faculty of Chemistry, Materials and Bioengineering, Kansai University, 3-3-35 Yamate-cho, Suita, Osaka 564-8680 (Japan)

Department of Chemistry and Materials Engineering, Faculty of Chemistry, Materials and Bioengineering, Kansai University, 3-3-35 Yamate-cho, Suita, Osaka 564-8680 (Japan)Search for more papers by this author
First published: 12 March 2015
Citations: 11

CD=Circular dichroism.

Graphical Abstract

Natural response: New photo-responsive amino acid derived azobenzenedicarboxylic acid derivatives (S)-1 ae were synthesized. Compound (S)-1 a in the trans form exhibited no circular dichroism (CD) signal in DMF under ambient conditions, whereas an intense Cotton effect was observed upon UV irradiation. The ESI mass spectrum of analogue derivatives and a theoretical CD study revealed that (S)-1 a in the cis form should be present as a cyclic chiral dimer.

Abstract

A series of new photo-responsive amino acid-derived azobenzenedicarboxylic acid derivatives (S)-1 ae were synthesized. Compound (S)-1 a in the trans form exhibited no circular dichroism (CD) signal in DMF under ambient conditions, whereas intense Cotton effects were observed upon UV irradiation, indicating the formation of a chiral supramolecular structure in the cis form. The CD signals disappeared when trifluoroacetic acid (TFA) was added to the solution. The ester counterpart [(S)-1 a′] showed no CD signal. Hydrogen bonding between the carboxy groups seemed necessary for constructing the supramolecular structure. The kinetic studies of cis to trans isomerization of (S)-1 a demonstrated that the formation of a chiral supramolecule enhances the stability of the cis-azobenzene structure. The ESI mass spectrum of stilbenedicarboxylic acid (S)-4, an analogue of (S)-1 b, confirmed the formation of a dimer. A theoretical CD study revealed that (S)-1 a in the cis form should be present as a cyclic chiral dimer.