Host–Guest Molecular Interaction Enabled Separation of Large-Diameter Semiconducting Single-Walled Carbon Nanotubes

Semiconducting single-walled carbon nanotubes (s-SWCNTs) with a diameter of around 1.0–1.5 nm, which present bandgaps comparable to silicon, are highly desired for electronic applications. Therefore, the preparation of s-SWCNTs of such diameters has been attracting great attention. The inner surface of SWCNTs has a suitable curvature and large contacting area, which is attractive in host–guest chemistry triggered by electron transfer. Here we reported a strategy of host–guest molecular interaction between SWCNTs and inner clusters with designed size, thus selectively separating s-SWCNTs of expected diameters. When polyoxometalate clusters of ∼1 nm in size were filled in the inner cavities of SWCNTs, s-SWCNTs with diameters concentrated at ∼1.3–1.4 nm were selectively extracted with the purity of ∼98% by a commercially available polyfluorene derivative. The field-effect transistors built from the sorted s-SWCNTs showed a typical behavior of semiconductors. The sorting mechanisms associated with size-dependent electron transfer from nanotubes to inner polyoxometalate were revealed by the spectroscopic and in situ electron microscopic evidence as well as the theoretical calculation. The polyoxometalates with designable size and redox property enable the flexible regulation of interaction between the nanotubes and the clusters, thus tuning the diameter of sorted s-SWCNTs. The present sorting strategy is simple and should be generally feasible in other SWCNT sorting techniques, bringing both great easiness in dispersant design and improved selectivity.