Selective Chemistry of Single-walled Nanotubes - Reaction Mechanism

Reaction Mechanism

Diazonium reagent and SWNT reaction has a two step mechanism. First, the diazonium reagent adsorbs noncovalently to an empty site on the nanotube surface, forming a charge-transfer complex. This is a fast, selective noncovalent adsorption and diazonium group in this complex partially dopes the nanotube, diminishing the tangential mode in the Raman spectrum. Desorption of A from nanotube is negligible (k-1 ~ 0). In second step complex B then decomposes to form a covalent bond with the nanotube surface. This is a slower step that need not be selective and is represented by the restoration of the G peak and increase in the D band.

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