Ferrocenylethynyl-terminated azobenzenes: synthesis, electrochemical, and photoisomerization studies

Chem Asian J. 2015 Mar;10(3):614-21. doi: 10.1002/asia.201403327. Epub 2015 Jan 29.

Abstract

Ferrocenylethynyl-terminated derivatives 8-12 have been synthesized and characterized by electrochemistry and UV/Vis spectroscopy. The electrochemical and photophysical studies indicate that the electronic communication in ferrocenylethynyl-substituted derivatives is strongly influenced by the substituted position of the ferrocenylethynyl moiety. In situ electrochemical oxidation or chemical oxidation caused a characteristically weak ligand-to-metal charge-transfer (LMCT) band to appear at 700-1000 nm. Subsequent electrochemical reduction or chemical reduction recovered the most of the original curve and the color of the solution as well. Among the derivatives, compound 8 exhibits the highest cis/trans molar ratio (64:36) in the photostationary state (PSS) upon light irradiation at 365 nm. Compound 8 exhibits excellent fatigue resistance and reversibility under several repeated reversible isomerization cycles.

Keywords: UV/Vis spectroscopy; azo compounds; electrochemistry; isomerization; redox chemistry.