1. pH Tuning of Water‐Soluble Arylazopyrazole Photoswitches
- Author
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Stefan Weber, Meral Ari, Karsten Parison, Paula Straub, Michael Walter, Simon Ludwanowski, Nils Pompe, Andreas Walther, and Somar Kalthoum
- Subjects
010402 general chemistry ,01 natural sciences ,Catalysis ,Photochromism ,Photoswitches | Hot Paper ,Thermal ,thermal half-life ,Full Paper ,arylazopyrazoles ,Photoswitch ,light-responsive system ,010405 organic chemistry ,business.industry ,Chemistry ,light-adaptive materials ,Organic Chemistry ,General Chemistry ,Full Papers ,photoswitches ,0104 chemical sciences ,Wavelength ,Orders of magnitude (time) ,Modulation ,Optoelectronics ,Density functional theory ,Transient (oscillation) ,business - Abstract
Arylazopyrazoles are an emerging class of photoswitches with redshifted switching wavelength, high photostationary states, long thermal half‐lives and facile synthetic access. Understanding pathways for a simple modulation of the thermal half‐lives, while keeping other parameters of interest constant, is an important aspect for out‐of‐equilibrium systems design and applications. Here, it is demonstrated that the thermal half‐life of a water‐soluble PEG‐tethered arylazo‐bis(o‐methylated)pyrazole (AAP) can be tuned by more than five orders of magnitude using simple pH adjustment, which is beyond the tunability of azobenzenes. The mechanism of thermal relaxation is investigated by thorough spectroscopic analyses and density functional theory (DFT) calculations. Finally, the concepts of a tunable half‐life are transferred from the molecular scale to the material scale. Based on the photochromic characteristics of E‐ and Z‐AAP, transient information storage is showcased in form of light‐written patterns inside films cast from different pH, which in turn leads to different times of storage. With respect to prospective precisely tunable materials and time‐programmed out‐of‐equilibrium systems, an externally tunable half‐life is likely advantageous over changing the entire system by the replacement of the photoswitch., Arylazopyrazoles are an emerging class of photoswitches with redshifted switching wavelength, high photostationary states, long thermal half‐lives and facile synthetic access. Understanding pathways for a simple modulation of the thermal half‐lives, while keeping other parameters of interest constant, is an important aspect for out‐of‐equilibrium systems design and applications. Here, it is demonstrated that the thermal half‐life of a water‐soluble PEG‐tethered arylazo‐bis(o‐methylated)pyrazole (AAP) can be tuned by more than five orders of magnitude using simple pH adjustment, which is beyond the tunability of azobenzenes.
- Published
- 2020
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