A review of the relationship between single-walled carbon nanotube molecular structures and their chemical reactivity Stephen A. Hodge,a Mustafa K. Bayazit,a Karl S. Colemanb and Milo S. P. Shaffer

Unweaving the rainbow: a review of the relationship betweensingle-walled carbon nanotube molecular structures and theirchemical reactivity

Stephen A. Hodge,a Mustafa K. Bayazit,a Karl S. Colemanb and Milo S. P. Shaffer*a

Chemical Society Review; Received 5th December 2011

DOI: 10.1039/c2cs15334c

Single-walled carbon nanotubes (SWNTs) are a fundamental family of distinct molecules, eachbearing the possibility of different reactivities due to their intrinsically distinct chemical properties.SWNT syntheses generate a heterogeneous mixture of species with varying electronic character,lengths, diameters and helicities, (n,m ), as well as other amorphous, graphitic and metal catalyst impurities. In recent years, selective syntheses and post-synthetic separation strategies haveadvanced, driven by the requirement for pure SWNTs displaying particular features. Covalentsurface modifications are widely-used to adapt SWNTs for specific applications with modifiedsolubility, compatibility and specific functionalities. In many cases, such reactions have beenfound to be selective, illuminating the fundamentally distinct chemistry of each (n,m) species. This differential reactivity has found immediate utility in facilitating the sorting of nanotubes according to specific diameter, electronic properties and, most importantly, helicity. In thistutorial review, we discuss a wide range of selective reactions, the mechanisms that are thought to govern selectivity, and the challenges of separating, characterising and regenerating themodified SWNTs.