Unusual concentration dependence of the photoisomerization reaction in donor-acceptor Stenhouse adducts

• Published in: Photochemical & photobiological sciences 2019-06, Vol.18 (6), p.1587-1595
• Main Authors: Lui, Brandon F, Tierce, Nathan T, Tong, Fei, Sroda, Miranda M, Lu, Hao, Read de Alaniz, Javier, Bardeen, Christopher J
• Format: Article
• Language: English
• Subjects: Actuation; Adducts; Biochemistry; Biomaterials; Chemistry; Dependence; Infrared spectra; Inhibition; Isomerization; Kinetics; Near infrared radiation; Photochromes; Photochromism; Physical Chemistry; Plant Sciences; Polymers; Reaction kinetics; Sample preparation; Switches
• ISSN: 1474-905X; 1474-9092
• DOI: 10.1039/c9pp00130a

Donor-acceptor Stenhouse adducts comprise a new class of reversible photochromic molecules that absorb in the visible and near-infrared spectral regions. Unimolecular photoisomerization reactions are usually assumed to be insensitive to photochrome density, at least up to millimolar concentrations. In this paper, the photoisomerization kinetics of a third-generation donor-acceptor Stenhouse adduct molecule (denoted DASA ) are examined over a range of concentrations. DASA switches efficiently at micromolar concentrations in both liquid solution and in polymers, but as the photochrome concentration is increased there is a dramatic inhibition of the photoisomerization. A kinetic study of both the reactant and photoproduct decays at varying concentrations and in different hosts indicates that the forward photoisomerization and the thermal backward reaction can change by factors of 20 or more depending on DASA concentration. Femtosecond transient absorption experiments show that the initial cis → trans step of the isomerization is not affected by concentration. It is hypothesized that long-range coulombic interactions interfere with the ground state electrocyclization stage of the isomerization, which is unique to the DASA family of photochromes. The physical origin of the inhibition of photoswitching at high photochrome concentrations must be understood if the DASA class of molecules is to be used for applications that require high photochrome concentrations, including photomechanical actuation. The isomerization rates of a photochromic donor-acceptor Stenhouse adduct depend on concentration. The net photoisomerization rate decreases with increasing concentration in liquids and polymers.