Cooperative Network Formation via Two-Colour Light-Activated λ-Orthogonal Chromophores.

Independently addressing photoreactive sites within one molecule with two colours of light is a formidable challenge. Here, we combine two sequence independent λ-orthogonal chromophores in one heterotelechelic dilinker molecule, to exploit their disparate reactivity utilizing the same reaction partner, a maleimide-containing polymer. We demonstrate that polymer network formation only proceeds if two colours of light are employed. Upon single colour irradiation, linker-decorated post-functionalized polymers are generated at either wavelength and in either sequence. Network formation, however, is only achieved by sequential or simultaneous two colour irradiation. The herein introduced photoreactive system demonstrates the power of wavelength orthogonal chemistry in macromolecular synthesis.