Modular Engineering of H-Bonded Supramolecular Polymers for Reversible Functionalization of Carbon Nanotubes

A. Llanes-Pallas, K. Yoosaf, H. Traboulsi, J. Mohanraj, T. Seldrum, J. Dumont, A. Minoia, R. Lazzaroni, N. Armaroli, D. Bonifazi,
J. Am. Chem. Soc. 2011, 133, 15412-15424
DOI: 10.1021/ja2011516

Abstract

A H-bond-driven, noncovalent, reversible solubilization/functionalization of multiwalled carbon nanotubes (MWCNTs) in apolar organic solvents (CHCl3, CH2Cl2, and toluene) has been accomplished through a dynamic combination of self-assembly and self-organization processes leading to the formation of supramolecular polymers, which enfold around the outer wall of the MWCNTs. To this end, a library of phenylacetylene molecular scaffolds with complementary recognition sites at their extremities has been synthesized. They exhibit triple parallel H-bonds between the NHN–NH (DAD) functions of 2,6-di(acetylamino)pyridine and the CO–NHCO (ADA) imidic groups of uracil derivatives. These residues are placed at 180° relative to each other (linear systems) or at 60°/120° (angular modules), in order to tune their ability of wrapping around MWCNTs. Molecular Dynamics (MD) simulations showed that the formation of the hybrid assembly MWCNT•[X•Y]n (where X = 1a or 1b -DAD- and Y = 2, 3, or 4 -ADA-) is attributed to π–π and CH−π interactions between the graphitic walls of the carbon materials and the oligophenyleneethynylene polymer backbones along with its alkyl groups, respectively. Addition of polar or protic solvents, such as DMSO or MeOH, causes the disruption of the H-bonds with partial detachment of the polymer from the CNTs, followed by precipitation. Taking advantage of the chromophoric and luminescence properties of the molecular subunits, the solubilization/precipitation processes have been monitored by UV–vis absorption and luminescence spectroscopies. All hybrid MWCNTs–polymer materials have been also structurally characterized via thermogravimetric analysis (TGA), transmission electron microscopy (TEM), atomic force microscopy (AFM), scanning tunneling microscopy (STM), and X-ray photoelectron spectroscopy (XPS).

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