Decoration of Polyfluorene-Wrapped Carbon Nanotubes with Photocleavable Side-Chains

Functionalizing polyfluorene-wrapped carbon nanotubes without damaging their properties is effective via Copper-Catalyzed Azide-Alkyne Cycloaddition (CuAAC). However, the length and nature of polymer side-chains can impact the conductivity of polyfluorene-SWNT films by preventing close contact between the nanotubes. Here, we investigate the functionalization of a polyfluorene-SWNT complex using photocleavable side-chains that can be removed post-processing. The cleavage of the side-chains containing an ortho-nitrobenzyl ether derivative is efficient when exposed to a UV lamp at 365 nm. The photoisomerization of the o-nitrobenzyl ether linker into the corresponding o-nitrosobenzaldehyde was first monitored via UV-Vis absorption spectroscopy and H-1-NMR spectroscopy on the polymer, which showed efficient cleavage after 2 h. We next investigated the cleavage on the polyfluorene-SWNT complex via UV-Vis-NIR absorption spectroscopy. The precipitation of the nanotube dispersion and the broad absorption peaks after overnight irradiation also indicated effective cleavage. In addition, Raman spectroscopy post-irradiation showed that the nanotubes were not damaged upon irradiation. This paper reports a proof of concept that may find applications for SWNT-based materials in which side-chain removal could lead to higher device performance.

Automated summary

Functionalization of polyfluorene-wrapped carbon nanotubes through Copper-Catalyzed Azide-Alkyne Cycloaddition (CuACC) without damaging their properties has been achieved. However, the conductivity of polyfluorene-SWNT films can be affected by the length and nature of polymer side-chains, hindering close contact between nanotubes. In this study, photocleavable side-chains were used to functionalize a polyfluorene-SWNT complex, which could be removed post-processing. Efficient cleavage of the side-chains containing an ortho-nitrobenzyl ether derivative was achieved under UV lamp exposure. The results demonstrate the potential of side-chain removal to improve device performance in SWNT-based materials.