Poly(2-Oxazoline) Amphiphilicity Tunes the Excited-State Proton Transfer of Pyrenol-Based Polyphotoacids.

Autor: Chettri A; Institute of Physical Chemistry, Friedrich Schiller University Jena, Helmholtzweg 4, 07743, Jena, Germany.; Research Department Functional Interfaces, Leibniz Institute of Photonic Technology, Albert-Einstein-Straße 9, 07745, Jena, Germany., Kaberov LI; Institute of Organic Chemistry and Macromolecular Chemistry, Friedrich Schiller University Jena, Humboldtstraße 10, 07743, Jena, Germany.; Jena Center for Soft Matter, Friedrich Schiller University Jena, Philosophenweg 7, 07743, Jena, Germany., Klosterhalfen N; Institute of Physical Chemistry, Friedrich Schiller University Jena, Helmholtzweg 4, 07743, Jena, Germany.; Research Department Functional Interfaces, Leibniz Institute of Photonic Technology, Albert-Einstein-Straße 9, 07745, Jena, Germany., Perera S; Institute of Organic Chemistry and Macromolecular Chemistry, Friedrich Schiller University Jena, Humboldtstraße 10, 07743, Jena, Germany.; Jena Center for Soft Matter, Friedrich Schiller University Jena, Philosophenweg 7, 07743, Jena, Germany., Jamshied M; Institute of Organic Chemistry and Macromolecular Chemistry, Friedrich Schiller University Jena, Humboldtstraße 10, 07743, Jena, Germany.; Jena Center for Soft Matter, Friedrich Schiller University Jena, Philosophenweg 7, 07743, Jena, Germany., Schacher FH; Institute of Organic Chemistry and Macromolecular Chemistry, Friedrich Schiller University Jena, Humboldtstraße 10, 07743, Jena, Germany.; Jena Center for Soft Matter, Friedrich Schiller University Jena, Philosophenweg 7, 07743, Jena, Germany., Dietzek-Ivanšić B; Institute of Physical Chemistry, Friedrich Schiller University Jena, Helmholtzweg 4, 07743, Jena, Germany.; Research Department Functional Interfaces, Leibniz Institute of Photonic Technology, Albert-Einstein-Straße 9, 07745, Jena, Germany.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Jul 05; Vol. 30 (38), pp. e202401047. Date of Electronic Publication: 2024 Jun 18.
DOI: 10.1002/chem.202401047
Abstrakt: The ability of light to change the properties of light-responsive polymers opens avenues for targeted release of cargo with a high degree of spatial and temporal control. Recently, we established photoacid polymers as light-switchable macromolecular amphiphiles. In these systems, light-induced excited-state proton transfer (ESPT) causes changes in amphilicity. However, as the intermolecular process itself critically depends on the local environment of the photoacid unit within the polymer, the overall amphiphilicity directly influences ESPT. Thus, understanding the impact of the local environment on the photophysics of photoacidic side chains is key to material design. In this contribution we address both thermodynamic and kinetic aspects of ESPT in oxazoline-based amphiphilic polymers with pyrenol-based photoacid side chains. We will compare the effect of polymer design, i. e. statistical and block arrangements, i. e. in poly[(2-ethyl-2-oxazoline)-co-(1-(6/8-hydroxyperene)sulphonylaziridine)] and poly(2-ethyl-2-oxazoline)-block-poly[(2-ethyl-2-oxazoline)-co-(2-(3-(6-hydroxypyrene)sulphonamide)propyl-2-oxazoline), on the intermolecular proton transfer reaction by combining steady-state and time-resolved absorption and emission spectroscopy. ESPT appears more prominent in the statistical copolymer compared to a block copolymer with overall similar pyrenol loading. We hypothesize that the difference is due to different local chain arrangements adopted by the polymers in the two cases.
(© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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