Abstract
In a systematic fashion, several methods for esterification and amidation of singleβwalled carbon nanotubes have been evaluated with focus on efficiency and reproducibility in forming covalently functionalized products soluble in organic media. The outcome of transformations was determined using IR, Raman and NMR spectroscopy and by thermogravimetric analysis (TGA). Amidation proceeding via a SWNTβ(COCl)~n~ intermediate yielded the expected covalent product, whereas carboxylate salt formation dominated with other attempted methods. Esterification was achieved via the acyl chloride method and via alkylation of SWNTβ(COO^β^)~n~, the latter being the more efficient method. A nonβcovalent solubilizing interaction was obtained for RNH~2~ but not for ROH (R = octadecyl), proving that the most important nonβcovalent interaction between oxidatively cleaned SWNTs and octadecylamine is a salt formation. The outcome of the secondary functionalization of carboxyl units is highly reproducible for experiments carried out on the same batch of SWNTβ(COOH)~n~. Normalization of the outcome of the secondary functionalization to the composition of the different batches of starting materials reveals an overall high reproducibility of the secondary functionalizations. The differences in outcome related to different commercial SWNT batches from the same synthetic procedure is negligible compared to that resulting from differences in overall carboxyl content after the primary HNO~3~ oxidative cleaning step. Hence, the composition of purified SWNT starting materials always needs to be assessed, in particular before drawing any conclusions concerning differences in outcome from reaction systems involving different sources of SWNT material. (Β© WileyβVCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)