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Wavelength-gated photoreversible polymerization and topology control

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Abstract

We exploit the wavelength dependence of [2 + 2] photocycloadditions and -reversions of styrylpyrene to exert unprecedented control over the photoreversible polymerization and topology of telechelic building blocks. Blue light (λmax = 460 nm) initiates a catalyst-free polymerization yielding high molar mass polymers (Mn = 60 000 g mol−1), which are stable at wavelengths exceeding 430 nm, yet highly responsive to shorter wavelengths. UVB irradiation (λmax = 330 nm) induces a rapid depolymerization affording linear oligomers, whereas violet light (λmax = 410 nm) generates cyclic entities. Thus, different colors of light allow switching between a depolymerization that either proceeds through cyclic or linear topologies. The light-controlled topology formation was evidenced by correlation of mass spectrometry (MS) with size exclusion chromatography (SEC) and ion mobility data. Critically, the color-guided topology control was also possible with ambient laboratory light affording cyclic oligomers, while sunlight activated the linear depolymerization pathway. These findings suggest that light not only induces polymerization and depolymerization but that its color can control the topological outcomes.

Graphical abstract: Wavelength-gated photoreversible polymerization and topology control

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Article information


Submitted
25 Oct 2019
Accepted
10 Feb 2020
First published
12 Feb 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020, Advance Article
Article type
Edge Article

Wavelength-gated photoreversible polymerization and topology control

H. Frisch, K. Mundsinger, B. L. J. Poad, S. J. Blanksby and C. Barner-Kowollik, Chem. Sci., 2020, Advance Article , DOI: 10.1039/C9SC05381F

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