Toward Negatively Curved Carbons

Abstract

Negatively curved carbons are theoretical carbon allotropes as proposed by embedding heptagons or octagons in a graphitic lattice. Unlike five-membered rings in fullerenes, which induce positive curvature, the seven- or eight-membered rings induce negative curvature, giving rise to a variety of esthetic carbon nanostructures known as Mackay crystals or carbon schwarzites. In addition, hypothetical toroidal carbon nanotubes consisting of five-, six-, and seven-membered rings present positive curvature on the outside and negative curvature on the inside of the torus. These carbon allotropes with negative curvature are predicted to have interesting properties and potential applications on the basis of computational studies but are yet to be synthesized. A promising bottom-up approach to these intriguing but still imaginary carbon structures is organic synthesis of negatively curved polycyclic arenes, which are also known as negatively curved nanographenes. They not only are segments of negatively curved carbon allotropes containing important structural information but also can in principle be used as templates or monomer units for the synthesis of carbon schwarzites and toroidal carbon nanotubes. This Account describes research on the design, synthesis, structure, stereochemical dynamics, and properties of negatively curved nanographenes, with emphasis on our efforts in this field. In our designs of negatively curved nanographenes, a few heptagon- or octagon-embedded π systems were employed as basic structural units, including [7]circulene, heptagon-embedded hexa- peri-benzocoronene, tetrabenzodipleiadiene, and [8]circulene. They present a saddle-shaped geometry and consist of a relatively small number of sp carbon atoms. By expanding or connecting these structural units, we designed and synthesized larger negatively curved nanographenes consisting of up to 96 sp carbon atoms. A method of key importance in the synthesis of negatively curved nanographenes is the Scholl reaction, which enables the formation of multiple carbon-carbon bonds in a single step by intramolecular oxidative cyclodehydrogenation. The unique structures of negatively curved nanographenes were studied by experimental and computational methods. In particular, X-ray crystallography of single crystals revealed remarkably curved π faces accompanied by severe out-of-plane deformation of benzenoid rings, which sheds light on the limit of π bonds and the aromaticity of polycycles. As found mainly from calculations, the flexible polycyclic frameworks of negatively curved nanographenes are associated with stereochemical dynamics that is not available for planar polycyclic aromatics. In addition, some negatively curved nanographenes have been found to function as organic semiconductors in the solid state. We envision that the study of negatively curved nanographenes will serve as an important initial step toward the eventual synthesis of new carbon allotropes with negative curvature and new frontiers of nanocarbon materials.

Polycyclic Aromatic Hydrocarbons as Potential Building Blocks for Organic Solar Cells

“…PAHs with odd‐membered rings, especially those possessing 5‐ or 7‐membered rings, are getting more and more popular due to the properties that arise from this structural change . For example, the introduction of odd‐membered rings in a six‐membered rings scaffold can induce a significant curvature to the PAH, allowing the synthesis of elegant yet useful molecules . Corannulene, which consists of a five‐membered ring surrounded by five six‐membered rings, is probably the most popular structure of all as it is the building block of fullerene C 60 .…”

Synthesis of Tribenzo[a,c,e]cyclooctene Oligomers: Toward Negatively Curved Nanocarbons

“…Negatively curved carbon allotropes are potentially a new frontier of carbon nanoscience after fullerenes, carbon nanotubes and graphene, but are yet to be synthesized. A promising bottom‐up approach to theoretical carbon allotropes of negative curvature is organic synthesis of heptagon or octagon‐embedded polycyclic arenes, which are segments of negatively curved carbon allotropes containing important structural information and thus are also known as negatively curved nanographenes. Moreover, they are envisioned as templates or monomer units for synthesis of negatively curved carbon allotropes in a controlled growth process or by polymerization, respectively .…”

Gram‐Scale Bottom‐Up Synthesis of Macrographene

“…Zhi and Müllen have classified polycyclic aromatic hydrocarbons (PAH) into molecular graphene (diameter less than 5 nm along the 2D direction), nanographene (diameter between 5 and 500 nm) and macrographene (MG, diameter more than 500 nm) . Large number of reports dealing with the bottom‐up synthesis of molecular and nanographenes have appeared recently . The bottom‐up syntheses generally involve preparation of suitably substituted oligophenylene or hexabenzocoronene precursors which are then converted to nanographenes by oxidative cyclodehydrogenation reaction.…”