Sidewall Amino-Functionalization of Single-Walled Carbon Nanotubes through Fluorination and Subsequent Reactions with Terminal Diamines

Abstract

Single-walled carbon nanotubes (SWNTs) with the N-alkylidene amino groups covalently attached to their side walls have been prepared starting from colloidal solutions of fluorinated SWNTs (fluoronanotubes) in terminal alkylidene diamines followed by heating at 70−170 °C. On the basis of data from thermal gravimetric and energy-dispersive X-ray analyses, the degree of SWNT functionalization achieved was estimated to be as high as 1 in 8 to 12 sidewall carbons. The demonstrated new C−N functionalization method provides a synthetic tool for binding amino acids, DNA, and polymer matrices to the side walls of the SWNTs as well as yields sidewall amino-functionalized nanotube precursors for the preparation of nylon−SWNT polymer materials.

Theoretical Studies of Substitutionally Doped Single-Walled Nanotubes

“…Chemical functionalization of carbon nanotubes can easily disrupt the extended conjugation and reduce the electrical conductivity along the axis of the tube. In particular, covalent modification of the sidewalls of carbon nanotubes has been achieved [3] via strategies including tandem fluorination/nucleophilic substitution [54][55][56], ozonolysis [57,58], Diels-Alder cycloaddition [59,60], osmylation [61], hydroboration [62], dissolving metal reduction (Billups reaction) [63], carbene addition [64], nitrene addition [65], dipolar cycloaddition of azomethine ylides [66], vinyl carbonylation via zwitterionic intermediates [67,68], other electrophilic oxidations [69], radical alkylation [64,70], perfluoroalkylation [71,72], and arylation [73]. Current technologies suffer from low reactivity and/or poor selectivity.…”

Mechanical Properties of Nanostructured Materials Determined Through Molecular Modeling Techniques

“…Single wall carbon nanotubes have been functionalized with amine groups. 2 Subsequently, nanocomposites were synthesized using these functionalized nanotubes in an epoxy matrix.…”

Organic semiconductors for device applications: current trends and future prospects

“…Additionally, C-F bonds, involved in fluorination, were relatively weaker than those of alkyl fluorides [157]. They, in turn, offered better substitution sites for additional functionalization [158] involving amino, alkyl, and hydroxyl groups [159,160]. Besides, other conjugation methods including the Diels-Alder reaction, carbene and nitrene addition [161][162][163], chlorination, bromination [164], hydrogenation [165], and azomethineylides [166] reactions were also explored successfully in this context.…”