Effect of Single-Walled Carbon Nanotube Association upon H NMR Spectra of Representative Organonitrogen Compounds

This report is important to achieving SWCNT solvation, understanding adsorption of molecules on SWCNT surfaces, and SWCNT characterization by NMR. Complexation of 1-methyl-2-pyrrolidone (NMP) and other selected organonitrogens with single-walled carbon nanotubes (SWCNTs) was studied by proton nuclear magnetic resonance (NMR). The magnitude of (1)H NMR chemical shift change upon SWCNT:organonitrogen complex formation represents the strength of the association. Magnitudes of changes in NMR signals of different protons in the organonitrogen reveal which protons are in close proximity to SWCNTs. Results reveal that (1) in amides and aminoketones, SWCNT association with carbonyls is stronger than with nitrogen, (2) in aminoalcohols, SWCNT association with nitrogen is stronger than with oxygen, and (3) protons bonded to heteroatoms have greater changes in their chemical shifts than those bonded to carbons. Changes (broadening and downfield shifts) in (1)H NMR signals of the organonitrogen compounds, which accompany SWCNT:organonitrogen association, are dependent upon (1) type of proton within R (α, β, etc.), (2) proximity to the carbonyl (R-CO versus NR(2)), (3) steric effects of alkyls, (4) electronic effects of alkyls, and (5) effects of tethering two ends of a molecule.