期刊
POLYMERS
卷 15, 期 5, 页码 -出版社
MDPI
DOI: 10.3390/polym15051306
关键词
photoswitch; thiol-ene; main-chain diazocine polymer; photochromism; hydrodynamic size expansion; DOSY NMR
In this study, linear photoresponsive poly(thioether)s containing diazocine moieties in the polymer backbone were synthesized and their photoisomerization behavior was investigated. The resulting polymers showed reversible photoswitchability between the (Z)- and (E)-configurations. The study highlights the potential use of diazocine as an elongating actuator in macromolecular systems and smart materials.
Unlike azobenzene, the photoisomerization behavior of its ethylene-bridged derivative, diazocine, has hardly been explored in synthetic polymers. In this communication, linear photoresponsive poly(thioether)s containing diazocine moieties in the polymer backbone with different spacer lengths are reported. They were synthesized in thiol-ene polyadditions between a diazocine diacrylate and 1,6-hexanedithiol. The diazocine units could be reversibly photoswitched between the (Z)- and (E)-configurations with light at 405 nm and 525 nm, respectively. Based on the chemical structure of the diazocine diacrylates, the resulting polymer chains differed in their thermal relaxation kinetics and molecular weights (7.4 vs. 43 kDa) but maintained a clearly visible photoswitchability in the solid state. Gel permeation chromatography (GPC) measurements indicated a hydrodynamic size expansion of the individual polymer coils as a result of the Z -> E pincer-like diazocine switching motion on a molecular scale. Our work establishes diazocine as an elongating actuator that can be used in macromolecular systems and smart materials.
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