Synthesis of a fullerene-based one-dimensional nanopolymer
through topochemical transformation of the parent nanowire (30 page pdf)
Large-scale practical applications of fullerene (C60) in nanodevices could be significantly facilitated if the commercially-available micrometer-scale raw C60 powder were further processed into a one-dimensional (1D) nanowire-related polymer displaying covalent bonding as molecular interlinks and resembling traditional important conjugated polymers. However, there has been little study thus far in this area despite the abundant literature on fullerene. Here we report the synthesis and characterization of such a C60-based nanowire polymer, (-C60TMB-)n, where TMB=1,2,4-trimethylbenzene, which displays a well-defined crystalline structure, exceptionally large length-to-width ratio and excellent thermal stability. The material is prepared by first growing the corresponding nanowire through a solution phase of C60 followed by a topochemical polymerization reaction in the solid state. Gas chromatography, mass spectrometry and 13C nuclear magnetic resonance evidence is provided for the nature of the covalent bonding mode adopted by the polymeric chains. Theoretical analysis based on detailed calculations of the reaction energetics and structural analysis provides an in-depth understanding of the polymerization pathway. The nanopolymer promises important applications in biological fields and in the development of optical, electrical, and magnetic nanodevices.
From MIT Technology Review Blog:
The exciting thing about this breakthrough is the potential to grow buckywires on an industrial scale from buckyballs dissolved in a vat of bubbling oil. Since the buckywires are insoluble, they precipitate out, forming crystals. (Here it ought to be said that various other groups are said to have made buckywires of one kind or another, but none seem to have nailed it from an industrial perspective.)
So what might buckywires be good for? First up is photovoltaics: these buckywires look as if they could be hugely efficient light harvesters because of their great surface area and the way that they can conduct photon-liberated electrons. Then there are various electronic applications in wiring up molecular circuit boards.
But perhaps the area of greatest interest is drug delivery. Geng and co suggest that buckywires ought to be safer than carbon nanotubes because the production method is entirely metal-free.
We have demonstrated for the first time an approach to the synthesis of a C60-based nanowire polymer and established the chemical bonding mode involved in the polymeric chains based on both experimental measurements and theoretical calculations. Importantly, the material adopts a crystalline 1D nanostructure which resembles carbon nanotubes in shape and other important conjugated polymers in structure. Since the material does not contain any metal but is simply composed almost entirely of carbon (while it contains hydrogen, the content is only 1.4 wt %), it suggests biological compatibility and it is, perhaps, even more attractive than carbon nanotubes for bio-applications. In addition, the material has further important potential for applications in photo-electrical devices because of the intrinsically large magnitude of the nonlinear optical response of C60 and the excellence of its photoinduced charge transfer properties. Considering all these, we believe that this work represents a step toward true applications of C60 in nanotechnology by the ability of processing commercially available raw C60 powder into a one-dimensional, crystalline, and covalently-bonded fullerene nanopolymer.
We consider that applications of the reported nanopolymer may be facilitated by a wet chemical approach through surface modification of the material using the rich chemistry of fullerene developed over the last 20 years. Since the nanopolymer is insoluble in common solvents, such surface modification or functionalization should be possible to achieve in either an aqueous or an organic solution without destructing its solid-state structure. Such a wet approach would benefit from low-cost processing, the need for only simple apparatus and the possibility of scaling-up to the industrial level. Moreover, the nanopolymer itself not only provides an example of phase transition of the parent nanowire driven by forming and breaking covalent bonds, but also illustrates the enduring significance of the original fullerene concept and its versatility as applied to new fullerene-related nanostructures. Finally, the host (C60) and guest (1,2,4-TMB) nature of the polymerization suggests a general host-guest route to the synthesis of new types of fullerene-based nanopolymers constructed by different organic monomers and fullerenes