A grafting-from strategy for the synthesis of bottlebrush nanofibers from organic semiconductors

Bottlebrush polymers with optoelectronic function show promise for applications in photonic crystals, nanomedicine, and encoding of information. In particular, bottlebrush polymers formed from organic semiconductors give wire-like nanoparticles where band gaps, fluorescence, and energy transfer can be tuned. To date, such bottlebrush polymers have largely been prepared by grafting-through polymerization of organic semiconductor macromonomers, where pre-synthesized side chains are polymerized along a bottlebrush backbone. While this approach provides high side-chain grafting densities, the length of bottlebrush polymers that is possible to obtain is limited by steric crowding at the propagating chain end. Here, we describe methods for preparing ultralong bottlebrush nanofibers from organic semiconductors, with backbone lengths approaching 800 repeating units and molecular weights in excess of 4 MDa. By combining reversible addition fragmentation chain transfer and Cu(0) reversible deactivation radical polymerization, a “grafting-from” protocol is described where monomers can be grown from a pre-synthesized backbone. Bottlebrush polymers were prepared from organic semiconductors used as n-type, p-type, and host materials in multilayer organic devices. Finally, a two-component bottlebrush polymer exhibiting deep blue emission, two-photon fluorescence, and a quantum yield of unity is also prepared by this method.