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Donor–Acceptor Stenhouse Adduct‐Polydimethylsiloxane‐Conjugates for Enhanced Photoswitching in Bulk Polymers
Author(s) -
Clerc Michèle,
Tekin Cem,
Ulrich Sebastian,
Freire Rafael V. M.,
Salentinig Stefan,
Bruns Nico,
Boesel Luciano F.
Publication year - 2022
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.202200120
Subject(s) - polymer , materials science , polydimethylsiloxane , conjugated system , glass transition , methacrylate , chemical engineering , lower critical solution temperature , click chemistry , polymer chemistry , nanotechnology , copolymer , composite material , engineering
Donor–acceptor Stenhouse adducts (DASAs) are a rapidly emerging class of visible light‐activated photochromes and DASA‐functionalized polymers hold great promise as biocompatible photoresponsive materials. However, the photoswitching performance of DASAs in solid polymer matrices is often low, particularly in materials below their glass transition temperature. To overcome this limitation, DASAs are conjugated to polydimethylsiloxanes which have a glass transition temperature far below room temperature and which can create a mobile molecular environment around the DASAs for achieving more solution‐like photoswitching kinetics in bulk polymers. The dispersion of DASAs conjugated to such flexible oligomers into solid polymer matrices allows for more effective and tunable DASA photoswitching in stiff polymers, such as poly(methyl methacrylate), without requiring modifications of the matrix. The photoswitching of conjugates with varying polymer molecular weight, linker type, and architecture is characterized via time‐dependent UV–vis spectroscopy in organic solvents and blended into polymethacrylate films. In addition, DASA‐functionalized polydimethylsiloxane networks, accessible via the same synthetic route, provide an alternative solution for achieving fast and efficient DASA photoswitching in the bulk owing to their intrinsic softness and flexibility. These findings may contribute to the development of DASA‐functionalized materials with better tunable, more effective, and more reversible modulation of their optical properties.