Isomerization, Protonation, and Hydrolysis Properties of Naphthalimide-Containing Spiropyran in Aqueous Media

• Published in: The Journal of Physical Chemistry B Vol. 128; no. 36; pp. 8797 - 8806
• Main Authors: Shiraishi, Yasuhiro, Oshima, Taku, Hirai, Takayuki
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society (ACS) 31.08.2024
• Subjects: absorption; ambient temperature; deprotonation; energy; hydrogen bonding; hydrolysis; isomerization; moieties; protonation; solvents; zwitterions
• ISSN: 1520-6106; 1520-5207; 1520-5207
• DOI: 10.1021/acs.jpcb.4c03894

Synthesis of spiropyrans exhibiting ring-opening/closing isomerization driven by external stimuli is a challenging subject for the development of molecular sensors. A napthalimide-containing spiropyran ( ) promotes rapid isomerization between the spirocyclic (SP) form and ring-opened merocyanine (MC) form by the change in solvent polarity even under the dark condition at room temperature. In this work, the effect of water on the isomerization behavior of was studied. The addition of water caused an MC-water H-bonding interaction and shifted the resonance MC structure to the zwitterionic form with a lower ground-state energy. The stabilized MC form promoted spontaneous SP → MC isomerization and increased the equilibrium MC concentration. The effect of pH on the behavior of was also studied. In acidic-neutral media, protonation/deprotonation of the naphthalimide moiety led to rapid and reversible changes in the absorption spectra. In contrast, strongly basic media (pH > 12) promoted irreversible base-catalyzed hydrolysis of the alkene moiety.