Fullerene polymer

An alternative approach envisages the stimulating idea to produce an all-carbon fullerene polymer in which adjacent fullerenes are linked by covalent bonds and align in well characterized one-, two- and tliree-dimensional arrays. Polymerization of [60]fullerene, with the selective fonnation of covalent bonds, occurs upon treatment under pressure and relatively high temperatures, or upon photopolymerization in the absence of a triplet quencher,... 

The C-C linkage in tire polymeric [60]fullerene composite is highly unstable and, in turn, tire reversible [2+2] phototransfonnation leads to an almost quantitative recovery of tire crystalline fullerene. In contrast tire similarly conducted illumination of [70]fullerene films results in an irreversible and randomly occurring photodimerization. The important aspect which underlines tire markedly different reactivity of tire [60]fullerene polymer material relative to, for example, tire analogous [36]fullerene composites, is tire reversible transfomration of tire fomrer back to the initial fee phase. 

Saito S, Umemoto K, Miyake T (2004) Electronic Structure and Energetics of Fullerites, Fullerides, and Fullerene Polymers 109 41-57 Sakata M, see TakataM (2004) 109 59-84... 

Fullerene polymers, 12 250-252 Fullerene pyrrolidine dicarboxylic acid (FDA), 17 57... 

Giacalone F, Martin N (2006) Fullerene Polymers Synthesis and Properties. Chem. Rev. 106 5136-5190. 

Krakovjak MG, Anufrieva EV, Anan eva TD et al. (2006) Water-soluble complexes of poly(N-vinylamides) of various structures with C60 and C70 fullerenes. Polym Sci Ser A. 48 590-595. 

Although there have been great advances in covalent functionalization of fullerenes to obtain surface-modified fullerene derivatives or fullerene polymers, the application of these compounds in composites still remains unexplored, basically because of the low availability of these compounds [132]. However, until now, modified fullerene derivatives have been used to prepare composites with different polymers, including acrylic [133,134] or vinyl polymers [135], polystyrene [136], polyethylene [137], and polyimide [138,139], amongst others. These composite materials have found applications especially in the field of optoelectronics [140] in which the most important applications of the fullerene-polymer composites have been in the field of photovoltaic and optical-limiting materials [141]. The methods to covalently functionalize fullerenes and their application for composites or hybrid materials are very well established and they have set the foundations that later were applied to the covalent functionalization of other carbon nanostructures including CNTs and graphene. 

It was found that the intercalation of Cgo fullerene by an alkali metal in stoichiometric ratio (1 1) gives rise to the formation of anion-radical salts, namely, KC50, RbCgg, and CsCgo (Bommeli et al. 1995, Btouet et al. 1996). On slow cooling of the intercalation products, [2 + 2] cycloaddition of the fullerene species that is neighboring a crystal lattice occurs. Linear chain fullerenic polymers are formed. These polymers are stable in air, insoluble in THF, and possess metallic conductivity. They depolymerize only on heating above 320°C. 

Since there are 30 double bonds to react in fullerene Cgo, the [2-1-2] cycloaddition of Cgo molecules at these bonds results in the formation of so-called fullerene polymers [19]. Although it seemed important to clarify the structure and properties of the most basic unit of these polymers such as dimers and trimers, the method for preparation of these polymers such as high-pres-sure/high-temperature treatment or photoirradiation was not suitable to stop the [2-1-2] reaction at the stage of dimerization or trimerization. 

Eklund PC, Rao AM (eds) (1999) Fullerene polymers and fuUerene polymer composites. Springer, Berlin Heidelberg New York... 

The affinity of Cgo towards carbon nucleophiles has been used to synthesize polymer-bound Cgo [120] as well as surface-bound Cjq [121]. Polymers involving G q [54, 68, 69] are of considerable interest as (1) the fullerene properties can be combined with those of specific polymers, (2) suitable fullerene polymers should be spin-coatable, solvent-castable or melt-extrudable and (3) fullerene-containing polymers as well as surface-bound Cgo layers are expected to have remarkable electronic, magnetic, mechanical, optical or catalytic properties [54]. Some prototypes of polymers or solids containing the covalently bound Cjq moiety are possible (Figure 3.11) [68,122] fullerene pendant systems la with Cjq on the side chain of a polymer (on-chain type or charm bracelet ) [123] or on the surface of a solid Ib [121], in-chain polymers II with the fullerene as a part of the main chain ( pearl necklace ) [123], dendritic systems III, starburst or cross-link type IV or end-chain type polymers V that are terminated by a fullerene unit For III and IV, one-, two-and three-dimensional variants can be considered. In addition, combinations of all of these types are possible. 

The smallest subimit of these fullerene polymers is the C j2o dimer [368], Synthesis and examination of the properties of this molecule are, therefore, of considerable interest. Beside the solid-state mechanochemical reaction of with KCN -described in Section 3.2.3 -the dimer Cj2o can be synthesized at 5 GPa and 200 °C in good yields from a bis(ethylene-difhio)TTF-C5Q complex [369]. Cj2o is a dark brown solid that is almost insoluble in most organic solvents. 1 ts solubility decreases with increasing purity of the sample this behavior is also known for pristine C q. 

Heterogeneous mixing of fullerenes and fullerene derivatives with Ji-conjugated polymers has been used to produce excellent materials for photovoltaic devices [141], Upon irradiation of fullerene/polymer blends, charge transfer from the polymer to occurs, resulting in efficient photoconductivities. Better behavior of fullerene derivatives than with pristine Cgg has been observed, and attributed to the improved miscibility of the functionalized species. 

Electronic Structure and Energetics of Fullerites, Fullerides, and Fullerene Polymers... 

Keywords High pressure Fullerene polymers Lattice structures Raman spectroscopy Intermolecular bonding... 

Key Words High-resolution NMR, INADEQUATE, ADEQUATE, Carbon-carbon coupling constants, Long-range couplings, Double-quantum coherence, 13C NMR, 15N NMR, 29Si NMR, 77Se NMR, Fullerenes, Polymers, Review. 

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