Interlocking of Single-Walled Carbon Nanotubes with Metal-Tethered Tetragonal Nanobrackets to Enrich a Few Hundredths of a Nanometer Range in Their Diameters.

We have separated carbon nanotubes through host-guest complexation using host molecules named "nanotweezers" and "nanocalipers". In this work, a host molecule named tetragonal "M-nanobrackets", consisting of a pair of dipyrrin nanocalipers corresponding to two brackets "[" and "]" tethered by two metals (M), is designed, synthesized, and employed to separate single-walled carbon nanotubes (SWNTs). A facile three-step process including one-pot Suzuki coupling is developed to synthesize M-nanobrackets in a 37% total yield (M = Cu). Upon extraction of SWNTs with a square nanobracket and Cu(II), in situ formed tetragonal M-nanobrackets are found to interlock SWNTs to disperse them in 2-propanol. The interlocking is confirmed by absorption and Raman spectroscopy as well as transmission electron and atomic force microscopy. Especially, Raman spectroscopy is utilized to prove the interlocking of SWNTs; Cu-nanobrackets are found to show inherent resonance Raman signals and affect the SWNT signals, or a radial breathing vibration, due to the rigid rectangular structure of Cu-nanobrackets. The interlocking is facilely and thoroughly released through demetalation to recover the pristine SWNTs as well as the square nanobracket. Such chemically controlled locking and unlocking for SWNTs are one of the characteristics of our separation process. This enables a precise evaluation by Raman, photoluminescence, and absorption spectroscopy of the diameter selectivity to SWNTs, revealing the diameter enrichment of only three kinds of SWNTs, (7,6), (9,4), and (8,5), in the 0.02 nm diameter range from 0.90 to 0.92 nm among ∼20 kinds of SWNTs from 0.76 to 1.17 nm in their diameter range.