Hydrogen‐Bonding Donor‐Acceptor Stenhouse Adducts. Issue 6 (11th February 2020)

• Record Type: Journal Article
• Authors: Mallo, Neil; Tron, Arnaud; Andréasson, Joakim; Harper, Jason B.; Jacob, Lorrie S. D.; McClenaghan, Nathan D.; Jonusauskas, Gediminas; Beves, Jonathon E.
• Is Part Of: ChemPhotoChem. Volume 4:Issue 6(2020)
• Page Start: 407
• Page End: 412
• Publication Date: 2020-02-11
• Subjects: host-guest systems -- hydrogen bonding -- kinetics -- photochromism -- photoswitching; Photochemistry -- Periodicals; Periodicals; Electronic journals; 541.35
• DOI: 10.1002/cptc.201900295
• Languages: English
• ISSNs: 2367-0932

Abstract

Abstract: The binding of donor‐acceptor Stenhouse adducts (DASAs) bearing hydrogen‐bond recognition groups by Hamilton‐type receptors significantly influenced their photoswitching properties by altering thermal barriers to isomerization. The thermal barrier between the most stable linear isomer and the photogenerated isomer is lowered on binding to a receptor, and this barrier is crucial for switching properties. The thermal isomerization was shown to proceed via a stepwise linear‐ enol ‐ keto mechanism in DMSO where the tautomerisation barrier is within 2 kJ ⋅ mol −1 of that of the rate‐determining step, which may be important for analyzing switching properties. Abstract : An excellent host : A series of visible‐light responsive photoswitches in which the switching properties are controlled by hydrogen bonding interactions are prepared. The mechanism of thermal isomerization was shown to proceed via a stepwise linear enol ‐ keto mechanism.