Thiazolylazopyrazoles as Nonsymmetric Bis‐Heteroaryl Azo Switches: High‐Yield Visible‐Light Photoisomerization and Increased Z‐Isomer Stability by o‐Carbonylation

Following the progress on mono-heteroaryl azo switches (Het-N=N-Ph), a few bis-heteroaryl azo switches (Het-N=N-Het) have been studied recently, whereas the nonsymmetric bis-heteroaryl ones (Het1 -N=N-Het2 ) that can combine the respective merits of each heterocycle, have received little attention. Here we report thiazolylazopyrazoles as nonsymmetric bis-heteroaryl azo switches that combine the visible-light switching character of the thiazole ring and the ease of o-substitution of the pyrazole ring. Thiazolylazopyrazoles can achieve (near-)quantitative visible-light isomerization in both directions and long Z-isomer thermal half-lives of several days. In contrast to the drastically destabilizing effect of o-methylation, o-carbonylation of the pyrazole ring can remarkably stabilize Z isomers by inducing attractive intramolecular interactions (dispersion, C-H⋅⋅⋅N bond, and lone-pair⋅⋅⋅π interaction). Our work highlights the importance of the rational combination of two heterocycles and suitable structural substitution in developing bis-heteroaryl azo switches.