Selective Metallic Tube Reactivity in the Solution-Phase Osmylation of Single-Walled Carbon Nanotubes

Single-walled carbon nanotubes have been reacted with osmium tetroxide (OsO(4)) in solution in the presence of O(2) and UV irradiation at 254 nm. We observe one main structural motif, namely thickly coated nanotube structures, densely covered with OsO(2), consisting of multiple bundles of derivatized tubes. In a few instances, bridging uncoated tubes, connecting these thickly coated structures, incorporate a number of smaller nanotube bundles, projecting out from the larger functionalized aggregates of tubes. It is believed that OsO(2) (a) initially forms on the nanotubes by the preferential covalent sidewall functionalization of metallic nanotubes and (b) subsequently self-aggregates. The formation of an intermediate charge-transfer complex is likely the basis for the observed selectivity and reactivity of metallic tubes. Extensive characterization of these osmylated adducts has been performed using a variety of electron microscopy and optical spectroscopy techniques.