Contemporary catalyst-free photochemistry in synthetic macromolecular science

The spatiotemporal control that light affords the polymer chemists is one of the most powerful tools at their disposal. Photochemistry has been an integral part to the development of polymer science almost since its inception. Over the last half century, photochemistry has slowly developed into two sub-groups –catalyzed and noncatalyzed photochemistry. Herein, the current state-of-the-art with regard to the design, synthesis, and implementation of non-catalyzed photoactive moieties within macromolecules is outlined. We additionally summarize the current challenges and future outlook for the field of non-catalyzed macromolecular photochemistry including the design and implementation of red-shifted photoactive moieties, elucidating the complex nature of photoexcited states, and the ultimate goal of achieving perfectly wavelength independent ligations in order to create and manipulate intricate macromolecular architectures.