Effects of the chemical structure of polyfluorene on selective extraction of semiconducting single-walled carbon nanotubes

The selective recognition/extraction of semiconducting (sem)- and metallic (met)-single-walled carbon nanotubes (SWNTs) is still a great challenge in the science and technology of carbon nanotubes because their selective synthesis is still difficult. Poly(9,9-dioctyl-fluorene-2,7-diyl) (2C8-PF) and its derivatives are widely used polymers in carbon nanotube science and technology since they only extract sem-SWNTs from the mixture of sem-/met-SWNTs, while the separation mechanism is still unclear. In this study, we focus on the alkyl chain number on the polyfluorenes (PFs) to understand the mechanism for selective recognition. Here we describe the synthesis of mono-octyl moiety-carrying polyfluorene (poly(9-octyl-9H-fluorene-2,7-diyl), C8H-PF), and characterized its selective SWNT recognition/extraction ability, and found that the C8H-PF solubilized sem-SWNTs with a diameter of 0.9-1.1 nm, whose behavior is similar to that of 2C8-PF. In addition, C8H-PF selectively extracted sem-SWNTs with larger diameters (average diameter = 1.4 nm), whose behavior is different from that of 2C8-PF. Molecular mechanics simulations were carried out to understand such specific solubilization behavior. This study provides an insight into the design and synthesis of PF-based polymers and copolymers that exhibit efficient selective sem-SWNT recognition/extraction ability and their applications.