The first derivatives of Y(3)N@C(80) have been synthesized and fully characterized. 1,3-Dipolar cycloaddition of N-ethylazomethine ylide yielded mainly the pyrrolidine monoadduct of the icosahedral (I(h)()) symmetry cage exclusively at a [6,6] double bond. The same regioselectivity on a [6,6] double bond was observed when the endohedral compound was cyclopropanated with diethyl bromomalonate. These results are in pronounced contrast to those observed for icosahedral symmetry Sc(3)N@C(80), for which all reported derivatives add completely regioselectively to [5,6] double bonds. (1)H NMR, (13)C NMR, and HMQC spectroscopy revealed that the addition pattern on Y(3)N@C(80) resulted in a pyrrolidinofullerene derivative with unsymmetric pyrrolidine carbons and symmetric geminal protons. The cyclopropanated monoadduct exhibited symmetric ethyl groups on the malonate, consistent with regioselective addition at a [6,6] double bond. Attempts to perform the same cyclopropanation reaction on (I(h)()) Sc(3)N@C(80) failed to yield any identifiable products. These observations clearly indicate that the reactivity of trimetallic nitride endohedral metallofullerenes toward exohedral chemical functionalization is profoundly affected and effectively controlled by the nature of the endohedral metal cluster.

Lipophilic and hydrophilic dendra which are terminated with long alkyl chains and oligomeric poly(ethylene glycol) moieties, respectively, were synthesized, and these dendron species were used to functionalize single-wall (SWNT) and multiple-wall (MWNT) carbon nanotubes via amidation and esterification reactions. The functionalized carbon nanotube samples are, depending on the functionalities, soluble in common organic solvents, such as hexane and chloroform, and water to form colored homogeneous solutions. Characterizations using NMR, electron microscopy, and optical spectroscopic techniques show that the homogeneous solutions contain carbon nanotubes. A preliminary understanding of the structural features and properties of these soluble dendron-functionalized SWNTs and MWNTs is discussed in terms of results from the characterizations, the defunctionalization reactions, and the trapping of metal nanoparticles by the functionalized nanotubes in solution.

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The first pyrrolidine adduct on Sc(3)N@C(80) was synthesized and fully characterized. Addition of the N-ethylazomethine ylide occurs regioselectively on a [5,6] double bond on the surface of the icosahedral symmetry Sc(3)N@C(80), exactly in the same position as that described previously for a Diels-Alder adduct of the same compound.(11a,b) This addition pattern results in symmetric pyrrolidine carbons and unsymmetric geminal hydrogens on the pyrrolidine ring, as confirmed by (1)H and (13)C NMR spectroscopy, especially by HMQC. The shielding environment experienced by these geminal hydrogens differs by 1.26 ppm, indicative of pronounced ring current effects on the surface of this endohedral fullerene. This represents the first fully characterized pyrrolidine adduct on an endohedral metallofullerene.

In the preparation of high-quality polymeric carbon nanocomposites, the full compatibility of carbon nanotubes as the filler with the matrix polymer is required. For such a purpose, an amino-terminated polyimide, specifically designed to be structurally identical to the matrix polymer, was synthesized and used in the functionalization of carbon nanotubes. The functionalized carbon nanotube samples were analyzed and studied by using a series of techniques, and the results are presented and discussed. These nanotube samples and the matrix polyimide are soluble in the same organic solvents, allowing their intimate mixing in solution and the subsequent fabrication of polyimide-carbon nanotube composite films via wet-casting. According to results from the spectroscopic and electron microscopic characterizations, the carbon nanotubes are homogeneously dispersed in the nanocomposite films.