Topologically Unique Molecular Nanocarbons.

As new forms of carbon are unearthed, they invariably transform the scientific landscape. Numerous researchers have been inspired to discover the unique characteristics of these fascinating materials, consistently leading to the development of important technological innovations in materials science. Recently, studies on the preparation of molecular nanocarbons (small molecule analogues of larger carbon nanostructures) by precision organic synthesis have attracted much attention. Cycloparaphenylene (CPP), the substructure of carbon nanotubes (CNTs), is the oldest of such organic molecules, and since 2008 the successful synthesis of CPP dramatically advanced the synthetic chemistry of molecular nanocarbons. In fact, as pioneering research, we succeeded in producing carbon nanotubes using seed CPP molecules in 2013. This method represented an important landmark in the quest for controlling the diameter of CNTs via utilization of a well-defined small molecule as a template. Other avenues of research on graphene nanoribbons and partial structures of fullerenes such as corannulene and sumanene are also highly active at the current time. On the other hand, carbon forms with nontrivial topologies, i.e., topological nanocarbons, are virtually unexplored. In addition to the 3D network structures represented by the Mackay crystal, many topologically complex structures have been envisioned. To date, there is no rational approach toward the bottom-up synthesis of these carbon structures. As with the case of fullerenes and CNTs, access to these unique carbon structures should undoubtedly revolutionize a wide range of sciences. This Account highlights our efforts toward the synthesis of topologically unique molecular nanocarbons. Starting from CPP as the topologically simple subunit, we have successfully created novel molecular nanocarbons that have more complexed topologies. The first topic is carbon nanobelts, fully fused cylinder-shaped molecular nanocarbons representing the segment structure of armchair-type CNTs. The second topic is carbon nanocages, molecular nanocarbons having a "three-holed" topology representing the joint unit of branched CNTs. The third and fourth topics are all-benzene catenanes consisting of two CPP rings and an all-benzene trefoil knot topologically related to a carbon nanotorus. The world of nanocarbon molecules is only limited by our imagination and creativity. As history has proved, the synthesis of new forms of carbon and topologically complex molecules has always subsequently led to new fields and applications associated with their unforeseen properties and functions.