Effect of ring rize on photoisomerization properties of stiff stilbene macrocycles

• Main Authors: Sandra Olsson, Óscar Benito Pérez, Magnus Blom, Adolf Gogoll
• Format: Article
• Language: English
• Published: Beilstein-Institut 2019-10-01
• Series: Beilstein Journal of Organic Chemistry
• Subjects: dft; molecular mechanics; photostability; photo-switch; ring-strain; stiff stilbene
• Online Access: https://doi.org/10.3762/bjoc.15.233

A series of stiff stilbene macrocycles have been studied to investigate the possible impact of the macrocycle ring size on their photodynamic properties. The results show that reducing the ring size counteracts the photoisomerization ability of the macrocycles. However, even the smallest macrocycle studied (stiff stilbene subunits linked by a six carbon chain) showed some degree of isomerization when irradiated. DFT calculations of the energy differences between the E- and Z-isomers show the same trend as the experimental results. Interestingly the DFT study highlights that the energy difference between the E- and Z-isomers of even the largest macrocycle (linked by a twelve carbon chain) is significantly higher than that of the stiff stilbene unit itself. In general, it is indicated that addition of even a flexible chain to the stiff stilbene unit may significantly affect its photochemical properties and increase the photostability of the resulting macrocycle.