Single-walled carbon nanotubes (SWCNTs) are synthesized as mixtures of various SWCNT types, exhibiting drastically different properties, and thereby making the material of limited use. Fluorene-based polymers are successful agents for purifying such blends by means of conjugated polymer extraction (CPE), greatly increasing their application potential. However, a limited number of studies have devoted attention to understanding the effects of the polyfluorene backbone and side chain structure on the selectivity and separation efficiency of SWCNTs. Regarding the impact of the polymer backbone, it was noted that the ability to extract SWCNTs with conjugated polymers could be significantly enhanced by using fluorene-based copolymers that exhibit dramatically different interactions with SWCNTs depending on the types of monomers combined. However, the role of monomer side chains remains much less explored, and the knowledge generated so far is fragmentary. Herein, we present a new approach to tailor polymer selectivity by creating copolymers of polyfluorene bearing mixed-length alkyl chains. Their thorough and systematic analysis by experiments and modeling revealed considerable insight into the impact of the attached functional groups on the capacity of conjugated polymers for the purification of SWCNTs. Interestingly, the obtained results contradict the generally accepted conclusion that polyfluorene-based polymers and copolymers with longer chains always prefer SWCNTs of larger diameters. Besides that, we report that the capacity of such polymers for sorting SWCNTs may be considerably enhanced using specific low molecular weight compounds. The carried-out research provides considerable insight into the behavior of polymers and carbon-based materials at the nanoscale.
