Large π-Extended and Curved Carbon Nanorings as Carbon Nanotube Segments.

Abstract

ConspectusDesigning and synthesizing topologically unique molecules is a long-term challenge for synthetic chemists. Classical polycyclic aromatic hydrocarbons (PAHs) are a large group of π-conjugated planar organic compounds with rich photophysical and electronic properties, while nonplanar/curved PAHs have different molecular orbital arrangements and demonstrate unique properties. The chemistry of curved aromatic molecules has been of significant interest to explore the relationship between π conjugation and molecular geometry, which offers an attractive combination of fundamental problems, potential applications, and aesthetic appeal. Remarkable advances have been made in the last few decades during the discovery of novel curved aromatic molecules, including corannulenes, fullerenes, and carbon nanotubes (CNTs). Especially, there has been increasing interest in making single-chirality CNTs and their curved molecular components (known as finite segments of CNTs) with a fixed geometry. The most representative examples of such organic molecules are cycloparaphenylenes (CPPs) and related carbon nanorings, which possess cylindrical topologies and nanoscale conjugated segments similar to CNTs. CPPs, as the shortest cross-section and the simplest structure of armchair CNTs, have been synthetically accessible since 2008. Recent years have witnessed breakthroughs and rapid development in the synthesis of CPP-based nanorings as well as their derived molecules. In these molecules, the distortion from aromatic planarity can induce radially oriented π systems and further affect their electronic, optical, self-assembly, and charge-transport characteristics. These unique and interesting carbon nanorings are potentially useful in a variety of optoelectronic and biomedical materials. It is well-known that extension of the π-conjugated system facilitates the delocalization of π electrons and the redistribution of electronic clouds, leading to rich diversification of physical properties in the fields of electronics, optics, and supramolecular chemistry. Therefore, the precise design and controllable synthesis of carbon nanorings with large π conjugation will promote important advances in synthetic chemistry. To date, a number of π-extended carbon nanorings have been reported, and they exhibit novel physicochemical properties resulting from their fascinating topologies and structures. However, challenges still remain in the synthesis of π-extended carbon nanorings and their structural analogues and exploration of their unique properties.In this Account, we give a brief overview of our efforts to synthesize large π-extended carbon nanorings using different strategies and explore their novel applications. In 2013 we started our research on the synthesis of carbon nanorings with large π-conjugated structures. This research project has led to (i) the successful preparation of a series of carbon nanorings with inserted PAHs, especially with various nanographenes inserted, such as hexa-peri-hexabenzocoronene; (ii) the design and synthesis of a series of carbon nanorings consisting solely of PAHs; and (iii) the initial synthesis of π-extended carbon-nanoring-based polymers as the long polymeric segments of CNTs, in which macrocyclic CPPs as the basic repeating blocks were covalently coupled together. Herein we describe in detail how these challenging π-extended carbon nanorings were synthesized, and their interesting physical properties are discussed.