Reversible Photoreduction as a Trigger for Photoresponsive Gels

Emily R. Draper; Ralf Schweins; Riaz Akhtar; Philip Groves; Victor Chechik; Martijn A. Zwijnenburg; Dave J. Adams

doi:10.1021/acs.chemmater.6b02677

Reversible Photoreduction as a Trigger for Photoresponsive Gels

Emily R. Draper, Ralf Schweins, Riaz Akhtar, Philip Groves, Victor Chechik, Martijn A. Zwijnenburg, Dave J. Adams^*

^*Corresponding author for this work

Chemistry

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Abstract

We present here a new type of photoresponsive, reversible low molecular weight gel. All previous examples rely on a photoisomerisation, ring-closing or dimerization. We show that photoreduction of a perylene bisimide gelator results in the formation of a stable radical anion. The formation of the radical anion results in a change in the packing of the perylene bisimides in the self-assembled aggregates, leading to a change in fibrous network and an increase in the rheological properties of the gels. An increase in the rheological properties is extremely rare for a photoresponsive gel; normally, irradiation results in a gel-to-sol transition, and the gel falling apart. As the radical anion decays, which takes several hours in air, the original gel properties are restored. This photoreduction can be cycled many times. Finally, we show that the mechanical properties are different between irradiated and nonirradiated sections in a patterned gel.

Original language	English
Pages (from-to)	6336-6341
Number of pages	6
Journal	Chemistry of Materials
Volume	28
Issue number	17
Early online date	23 Aug 2016
DOIs	https://doi.org/10.1021/acs.chemmater.6b02677
Publication status	Published - 13 Sept 2016

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10.1021/acs.chemmater.6b02677

acs.chemmater.6b02677
© 2016 American Chemical Society
Final published version, 2.4 MBLicence: CC BY

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AU - Draper, Emily R.

AU - Schweins, Ralf

AU - Akhtar, Riaz

AU - Groves, Philip

AU - Chechik, Victor

AU - Zwijnenburg, Martijn A.

AU - Adams, Dave J.

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AB - We present here a new type of photoresponsive, reversible low molecular weight gel. All previous examples rely on a photoisomerisation, ring-closing or dimerization. We show that photoreduction of a perylene bisimide gelator results in the formation of a stable radical anion. The formation of the radical anion results in a change in the packing of the perylene bisimides in the self-assembled aggregates, leading to a change in fibrous network and an increase in the rheological properties of the gels. An increase in the rheological properties is extremely rare for a photoresponsive gel; normally, irradiation results in a gel-to-sol transition, and the gel falling apart. As the radical anion decays, which takes several hours in air, the original gel properties are restored. This photoreduction can be cycled many times. Finally, we show that the mechanical properties are different between irradiated and nonirradiated sections in a patterned gel.

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Reversible Photoreduction as a Trigger for Photoresponsive Gels

Abstract

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