Covalent Inter-Synthetic-Carbon-Allotrope Hybrids.

Abstract

Inter-synthetic-carbon-allotrope (SCA) architectures are constructed by hybridizing different types of carbon allotropes such as 0D-fullerene, 1D-carbon nanotubes (CNTs), and 2D-graphene. Also hybridizations of different fullerene families (e.g., empty fullerene, heterofullerenes, and endohedral fullerenes as well as their isomers) are considered as inter-SCA architectures and represent an emerging class of nanofunctional materials. Such highly integrated hybrids are quite promising, since they hold the potential of combining unique properties of each building block. For instance, hybridization of 2D-graphene, a synthetic carbon allotrope with outstanding chemical/physical properties, with 0D-fullerenes leads to materials with both outstanding solid state properties (e.g., electron mobility, flexibility, transparency, and mechanical stability) and distinct molecular properties (spatially resolved and tailor-made exohedral cage functionalization and endohedral guest encapsulation). Therefore, such integrated hybrids have potential as multifunctional nanocarbon materials applicable, for example, in energy storage, electronic devices, solar cells, or advanced sensors. Recognizing these significant advantages, a series of methods and techniques has been developed to synthesize such integrated hybrids. Based on in-depth understanding of fullerene chemistry, interfullerene hybrids where multiple fullerenes are linked together have been synthesized and fully characterized. However, due to the difficulty in functionalizing graphene or CNTs as a result of their poor dispersibility and weak reactivity the corresponding hybrids including these macromolecular forms are less explored. Furthermore, few approaches toward such systems reported so far inevitably involve some drawbacks such as low degree of addition and low production ability. This Account presents the concepts and strategies of our studies on the construction of inter-SCA hybrids. We first emphasize on our efficient "reductive functionalization route" as a versatile strategy for graphene/CNT functionalization. In sharp contrast to previous approaches, our strategy enables unprecedented functionalization of graphene/CNT without damaging their structures. As a consequence, the door for cross-dimensional architectures via hybridizing graphene/CNT with fullerenes has been opened. We will then summarize the diverse inter-SCA hybrids that we recently synthesized, ranging from interfullerene hybrids to those of cross-dimensional graphene/CNT-(endo)fullerenes hybrids as well as CNTs networks. For interfullerene hybrids, different types of fullerenes including empty fullerenes, heterofullerenes, and endohedral fullerenes have been employed. Finally, the prospects on the future challenges on inter-SCA hybrids are envisioned. This Account will provide fundamental insight into construction of inter-SCA hybrids and stimulate further efforts toward research on this emerging topic.