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Suspending Polyrotaxane Dissociation via Photo‐Reversible Capping of Terminals
Author(s) -
Arisaka Yoshinori,
Yui Nobuhiko
Publication year - 2019
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.201900323
Subject(s) - dissociation (chemistry) , materials science , photochemistry , polymer chemistry , chemistry , polymer science , chemical engineering , engineering
Reversible covalent bonds yield polymeric materials with functional characteristics such as self‐healing, shape memory, stress relaxation, and stimuli‐responsiveness. Here, photo‐reversibly cappable polyrotaxanes are designed and the on–off controlled dissociation of their supramolecular architectures is demonstrated. The polyrotaxanes are synthesized by capping dithiobenzoates at both terminals of polyethylene glycol threaded through multiple α‐cyclodextrins. Since dethreading of the α‐cyclodextrins is prevented by the dithiobenzoate stoppers, the supramolecular dissociation is induced by their photo‐cleavage. Subsequently, the cleaved dithiobenzoates spontaneously re‐cap the polyrotaxane terminals in darkness. Thus, the supramolecular dissociation can be modulated by photo‐reversible capping of the dithiobenzoate stoppers. These polyrotaxanes with dithiobenzoate stoppers are promising functional materials for photo‐controlling physical properties and structures.