Mixed-Solvent Engineering as a Way around the Trade-Off between Yield and Purity of (7,3) Single-Walled Carbon Nanotubes Obtained Using Conjugated Polymer Extraction.

The inability to purify nanomaterials such as single-walled carbon nanotubes (SWCNTs) to the desired extent hampers the progress in nanoscience. Various SWCNT types can be purified by extraction, but it is challenging to establish conditions giving rise to the isolation of high-purity fractions. The problem stems from the fact that common organic solvents or water cannot provide an optimal environment for purification. Consequently, one must often decide between the separation yield and purity of the product. This article reports how through the self-synthesis of poly(9,9-dioctylfluorene-alt-benzothiadiazole) with tailored characteristics, in-depth elucidation of the extraction process, and mixed-solvent engineering, a high-yield isolation of monochiral (7,3) SWCNTs is developed. The combination of toluene and tetralin affords a separation medium of unique properties, wherein both high yield and exceptional purity can be attained simultaneously. The reported results pave the way for further research on this rare chirality, which, as illustrated herein, is much more reactive than any of the previously separated SWCNTs.

ortho-Substituted Aryldiazonium Design for the Defect Configuration-Controlled Photoluminescent Functionalization of Chiral Single-Walled Carbon Nanotubes.

Defect functionalization of single-walled carbon nanotubes (SWCNTs) by chemical modification is a promising strategy for near-infrared photoluminescence (NIR PL) generation at >1000 nm, which has advanced telecom and bio/medical applications. The covalent attachment of molecular reagents generates sp3-carbon defects in the sp2-carbon lattice of SWCNTs with bright red-shifted PL generation. Although the positional difference between proximal sp3-carbon defects, labeled as the defect binding configuration, can dominate NIR PL properties, the defect arrangement chemistry remains unexplored. Here, aryldiazonium reagents with π-conjugated ortho-substituents (phenyl and acetylene groups) were developed to introduce molecular interactions with nanotube sidewalls into the defect-formation chemical reaction. The functionalized chiral SWCNTs selectively emitted single defect PL in the wavelength range of ∼1230-1270 nm for (6,5) tubes, indicating the formation of an atypical binding configuration, different from those exhibited by typical aryl- or alkyl-functionalized chiral tubes emitting ∼1150 nm PL. Moreover, the acetylene-based substituent design enabled PL brightening and a subsequent molecular modification of the doped sites using click chemistry.