Hydrogen-bonded metallo-supramolecular polymers based on ruthenium or iron complexes for the selective extraction of single-walled carbon nanotubes

The chemical functionalization of nano-carbon materials such as single-walled carbon nanotubes (SWNTs) and graphene by metal complexes has attracted much attention due to the multitude of potential applications in efficient energy-conversion and -storage devices. The solubilization and single-chiral...

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Published in:Dalton transactions : an international journal of inorganic chemistry 2018-10, Vol.47 (40), p.14195-14203
Main Authors: Oka, Shota, Ozawa, Hiroaki, Yoshikawa, Kai, Ikeda, Tomiki, Haga, Masa-Aki
Format: Article
Language:English
Subjects:
Carbon
Chemical bonds
Chemical synthesis
Chirality
Chlorobenzene
Coordination compounds
Electrodes
Energy storage
Graphene
Hydrogen bonding
Hydrogen storage
Iron
Liquid phases
Metallography
Morphology
Nanotubes
NMR
Nuclear magnetic resonance
Organic chemistry
Polymers
Raman spectra
Ruthenium
Single wall carbon nanotubes
Solubilization
Supramolecular polymers
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Summary:The chemical functionalization of nano-carbon materials such as single-walled carbon nanotubes (SWNTs) and graphene by metal complexes has attracted much attention due to the multitude of potential applications in efficient energy-conversion and -storage devices. The solubilization and single-chirality separation of SWNTs by surface modifications is a useful approach to manipulate SWNTs in the liquid phase. In this study, several Ru and Fe complexes containing two terminal quadruple hydrogen-bonded (H-bonded) ureidopyrimidinedione (UPy) groups were synthesized (Ru-1, Ru-UPy, and Fe-UPy) to form H-bonded supramolecular polymers by self-association. In order to control the solubility of these complexes in nonpolar solvents, Ru-UPy and Fe-UPy were endowed with long alkyl side chain groups in the coordinated 2,6-bis(benzimidazol-2-yl)pyridine ligand, while Ru-1 and Ru-2 do not contain such long alkyl chain groups. AFM measurements revealed that Ru-1, Ru-UPy, and Fe-UPy form a fiber-like network morphology on HOPG surfaces, arising from the H-bonded aggregation. However, only Ru-UPy and Fe-UPy are able to solubilize SWNTs effectively upon simple sonication in chlorobenzene. After the solubilization of a CoMoCAT® SWNT in chlorobenzene using Ru-UPy or Fe-UPy, UV-Vis-NIR spectra showed sharp peaks at 996 and 1150 nm, which were attributed to (6, 5) and (7, 6)-SWNTs. The Raman spectra of the solubilized SWNTs revealed peaks that were attributed to the radial breathing mode (RBM), which suggests an enrichment of semiconducting SWNTs, i.e., Ru-UPy and Fe-UPy are able to selectively solubilize semiconducting SWNTs. Cyclic voltammograms of films of SWNTs covered with Ru-UPy or Fe-UPy on ITO electrodes showed a well-defined adsorbed Ru(ii/iii) or Fe(ii/iii) wave. Upon addition of acid, the redox response from the adsorbed H-bonded Ru-UPy and Fe-UPy disappeared and only SWNTs were left on the ITO electrode. Moreover, the Ru-UPy/SWNT and Fe-UPy/SWNT hybrids exhibited non-linear I-V characteristics.
ISSN:1477-9226
1477-9234
DOI:10.1039/c8dt01573b