Dual-Stimuli Responsive Single-Chain Polymer Folding via Intrachain Complexation of Tetramethoxyazobenzene and β-Cyclodextrin

Lee, Daniel C.; Guye, Kathryn N.; Paranji, Rajan K.; Lachowski, Kacper; Pozzo, Lilo D.; Ginger, David S.; Pun, Suzie H.

doi:10.1021/acs.langmuir.1c01442

Title: Dual-Stimuli Responsive Single-Chain Polymer Folding via Intrachain Complexation of Tetramethoxyazobenzene and β-Cyclodextrin

Journal Article · 09 August 2021 · Langmuir

DOI: https://doi.org/10.1021/acs.langmuir.1c01442 · OSTI ID:1824173

Lee, Daniel C. ^[1]; Guye, Kathryn N. ^[2]; Paranji, Rajan K. ^[2]; Lachowski, Kacper ^[2];

^[2];

^[2]

Univ. of Washington, Seattle, WA (United States); University of Washington
Univ. of Washington, Seattle, WA (United States)

We synthesize and characterize a triblock polymer with asymmetric tetramethoxyazobenzene (TMAB) and β-cyclodextrin functionalization, taking advantage of the well-characterized azobenzene derivative-cyclodextrin inclusion complex to promote photoresponsive, self-contained folding of the polymer in an aqueous system. We use ¹H NMR to show the reversibility of (E)-to-(Z) and (Z)-to-(E) TMAB photoisomerization, and evaluate the thermal stability of (Z)-TMAB and the comparatively rapid acid-catalyzed thermal (Z)-to-(E) isomerization. Important for its potential use as a functional material, we show the photoisomerization cyclability of the polymeric TMAB chromophore and calculate isomerization quantum yields by extinction spectroscopy. To verify self-inclusion of the polymeric TMAB and cyclodextrin, we use two-dimensional ¹H NOESY NMR data to show proximity of TMAB and cyclodextrin in the (E)-state only; however, (Z)-TMAB is not locally correlated with cyclodextrin. Lastly, the observed decrease in photoisomerization quantum yield for the dual-functionalized polymer compared to the isolated chromophore in an aqueous solution confirms TMAB and β-cyclodextrin not only are in proximity to one another, but also form the inclusion complex.

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Research Organization:: Univ. of Washington, Seattle, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019288

OSTI ID:: 1824173

Journal Information:: Langmuir, Journal Name: Langmuir Journal Issue: 33 Vol. 37; ISSN 0743-7463

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Title: Dual-Stimuli Responsive Single-Chain Polymer Folding via Intrachain Complexation of Tetramethoxyazobenzene and β-Cyclodextrin

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