Synthesis of Cycloparaphenylenes and Related Carbon Nanorings: A Step toward the Controlled Synthesis of Carbon Nanotubes

Since their discovery in 1991, carbon nanotubes (CNTs) have attracted significant attention because of their remarkable mechanical, electronic, and optical properties. Structural uniformity of the CNT is critically important because the sidewall structures (armchair, zigzag, and chiral) determine many of the significant properties of CNTs. Ideally researchers would synthesize CNTs with a defined target sidewall structure and diameter, but the current synthetic methods, such as arc discharge and chemical vapor deposition, only provide CNTs as the mixtures of various structures. Purification of these mixtures does not allow researchers to isolate a structurally uniform CNT, which is the bottleneck for fundamental studies and advanced applications of these materials. Therefore, the selective and predictable synthesis of structurally uniform CNTs would represent a critical advance in both nanocarbon science and synthetic chemistry. This Account highlights our efforts toward the bottom-up synthesis of structurally uniform carbon nanotubes (CNTs). We envisioned a bottom-up synthesis of structurally uniform CNTs through a controlled growth process from a short carbon nanoring (template) that corresponds to the target structure of CNTs. Our simple retrosynthetic analysis led to the identification of cycloparaphenylenes (CPPs), acene-inserted CPPs, and cyclacenes as the shortest sidewall segments of armchair, chiral, and zigzag CNTs, respectively. With this overall picture in mind, we initiated our synthetic studies of aromatic rings/belts as an initial step toward structurally uniform CNTs in 2005. This research has led to (i) a general strategy for the synthesis of CPPs and related carbon nanorings using cyclohexane derivatives as a benzene-convertible L-shaped unit, (ii) a modular, size-selective, and scalable synthesis of [n]CPPs (a shortest segment of armchair CNTs), (iii) the X-ray crystal structure analysis of CPPs, (iv) the design and synthesis of acene-inserted CPPs as the shortest segment of chiral CNTs, and (v) the first synthesis of cyclo-1,4-naphthylene, a π-extended CPP. We believe this work will serve as important initial steps toward a controlled synthesis of CNTs.