Custom sequences for polymers using visible light

The world is full of long, chain-like molecules known as polymers. Famous examples of "sequential" copolymers, i.e. polymers made of multiple building blocks (or "monomers") arranged in a specific order, include DNA, RNA and proteins; their specific structure imparts the vast range of molecular functionality that underpins biological activity. However, making sequential polymers from scratch is a tricky business. We can design special monomers that assemble in different ways, but the complex syntheses that are required limit their availability, scope and functionality.

To overcome these limits, a team led by Associate Professor Akiko Inagaki from the Department of Chemistry, Tokyo Metropolitan University, applied a light-sensitive catalyst containing iridium and palladium. By switching a light on and off, they were able to control the speed at which two different monomers, styrene and vinyl ether, become part of a polymer chain. When exposed to light, the styrene monomer was found to be incorporated into the copolymer structure much more rapidly than in the dark, resulting in a single copolymer chain with different compositions along its length. Parts that are rich in styrene are more rigid than those rich in vinyl ether; by using different on/off light sequences, they could create polymers with a range of physical properties e.g. different "glass transition" temperatures, above which the polymer becomes softer.

The newly developed process is significantly simpler than existing methods. The team also found that both types of monomer were built into the polymer via a mechanism known as "non-radical coordination-insertion"; this is a generic mechanism, meaning that this new method might be applied to make polymers using a wide range of catalysts and monomers, with the potential to overcome the limited availability of monomer candidates.