Two-colour light activated covalent bond formation

Abstract

We introduce a photochemical bond forming system, where two colours of light are required to trigger covalent bond formation. Specifically, we exploit a visible light cis/trans isomerization of chlorinated azobenzene, which can only undergo reaction with a photochemically generated ketene in its cis state. Detailed photophysical mapping of the reaction efficiencies at a wide range of monochromatic wavelengths revealed the optimum irradiation conditions. Subsequent small molecule and polymer ligation experiments illustrated that only the application of both colours of light affords the reaction product. We further extend the functionality to a photo reversible ketene moiety and translate the concept into material science. The presented reaction system holds promise to be employed as a two-colour resist.

Dual-wavelength photochemical systems open up new avenues for novel lithographic techniques but currently only few wavelength-orthogonal photoreactive compounds undergoing reversible photoreaction are known. Here, the authors exploit cis/trans photoisomerization of azobenzenes and demonstrate photoligation of the cis state with a photochemically generated ketene.