Open-cage fullerenes: towards the construction of nanosized molecular containers

Abstract

Open-cage fullerene derivatives have excited organic chemists' creativity over the past decade. These adducts, generated via consecutive cleavage of sigma- and pi-carbon-carbon bonds on the fullerene cage, allow small atoms or molecules to pass through their opening and be placed inside the cavity. Restoration of the ruptured fullerene back to the pristine fullerene cage affords the corresponding endohedral complexes. This "molecular surgery" approach has been proposed as an alternative to the synthesis of endohedral fullerenes via the conventional physical methods of production, which restrict the availability of endohedral fullerenes to milligram quantities after laborious isolation procedures. In this critical review, we survey all published techniques for the creation of an orifice, as well as for the expansion of an existing one, on the fullerene framework. Successful encapsulation experiments employing cage-opened fullerene derivatives are also comprehensively discussed (160 references).

Non-adiabatic ab initio molecular dynamics of supersonic beam epitaxy of silicon carbide at room temperature

“…47 However, we found that even this more accurate level of theory does not modify the previous picture, although we tested various impact angles, different surface impact sites, several orientations of the impinging molecule, and defects on the fullerene cage enhancing the reactivity, such as found in C 57, 58, 59 (Ref. 48) without finding appreciable changes in the energy required for breaking the cage.…”

Photooxidation studies on indene-C60 adducts

“…Although kinetic analysis should be performed, these calculation results show that the 6,6-bonds near the substituents may be the most oxidative moieties in ICMA. This suggestion can be supported by the fact that the oxidation of several fullerene derivatives proceeds near the substituents [24][25][26].…”

Solid State Physicochemical Properties and Applications of Organic and Metallo- Organic Fullerene Derivatives

“…In some cases some of the fullerene carbons are removed rather than substituted, resulting in socalled open-cage fullerenes where functionalization is accompanied by partial disruption of the carbon backbone. The carbon cage is "opened" by successive chemical reactions referred to collectively as "fullerene surgery", leading to covalent linking of heterospecies and even oligomers to adjacent carbon atoms of the parent fullerene [42,43,44,45,46].…”