Single‐walled carbon nanotube absolute‐handedness chirality assignment confirmation using metalized porphyrin's supramolecular structures via STM imaging technique

Abstract

This work reports confirmation of the experimental assignment of the absolute‐handedness chirality of single‐walled carbon nanotubes (SWNTs). This was achieved by applying the scanning tunneling microscopy (STM) imaging technique to a supramolecular composite consisting of a metalized porphyrin derivative (nickel‐5,15‐bisdodecylporphyrin [Ni‐BDP]) affixed to the surfaces of chiral‐concentrated SWNTs (with right‐handed helix P‐ and left‐handed helix M‐). On the basis of the handedness chirality, different chiral supramolecular structures of Ni‐BDP were observed on the surfaces of the two SWNT enantiomers. The incorporation of a metal center into the porphyrin ring did not significantly affect the SWNT absolute‐handedness chirality assignment, the large pi‐system porphyrin ring being the crucial factor. These findings will effectively pave the way towards the clear selective synthesis, separation, chemistry, and applications of SWNT enantiomers.

Spontaneous Deracemizations

“…Nanoparticle supramolecular chirality from achiral compounds observed by different microscopies such as discussed by the Liu group: (A) achiral porphyrin, (B) achiral porphyrin, (C) azobenzene supramolecular aggregate, and (D) achiral polydiacetylene film . Reproduced and adapted with permissions from ref , Copyright 2015 American Chemical Society; ref , Copyright 2003 Royal Society of Chemistry; ref , Copyright 2020 Wiley; ref , Copyright 2014 Wiley.…”

Identification of Supramolecular Structures of Porphyrin Polymer on Single-Walled Carbon Nanotube Surface Using Microscopic Imaging Techniques

“…However, in some images (i.e., a, b, d, e, g, and i), the polymer molecules are aligned in a regular pattern on the tube surface. For more confirmation, we have tried to identify the supramolecular structures of porphyrin polymers on SWNT surface using STM imaging technique as we did it using porphyrin monomer [ 10 , 31 ], but unfortunately, we could not as the polymer probably may form a complicated 2D structure which cannot be possibly identified using STM especially under ambient conditions. Therefore, it was worthy to use gold nanoparticles (AuNPs) as markers after anchoring with porphyrin molecules via coordination bonding to produce a porphyrin polymer/AuNPs/SWNT hybrid that can be possibly identified using HR-TEM as well as AFM with clearer images, which will be discussed in detail in the following section.…”

“…Porphyrins, related compounds, and other polymers become significant candidates in many potential applications (i.e., electronic devices, physics, and many materials science applications) [ 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 ] as they have remarkable physical and chemical features, in addition, they can be simply synthesized with a wide substituent range.…”

“…We have tried to identify the supramolecular structures of porphyrin polymers on SWNT surface using STM imaging technique as we did it using porphyrin monomer [ 10 , 31 ], but unfortunately, we could not as the polymer probably may form a complicated 2D structure which cannot be possibly identified using STM especially under ambient conditions.…”

Hybrid Nano Flake-like Vanadium Diselenide Combined on Multi-Walled Carbon Nanotube as a Binder-Free Electrode for Sodium-Ion Batteries

“…CNTs are widely investigated in various fields for their chemical stability, electrical conductivity, and large surface area, and are used as energy storage, electronics, etc. [ 20 , 21 ]. Research papers on improved characteristics of CNTs have been analyzed as functionalized covalent or non-covalent [ 22 ].…”