Chemists make first-ever ring of pure 18-atom ‘cyclocarbon’ that could be a step towards molecule-scale transistors

Posted: August 21, 2019 in Uncategorized
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by Davide Castelvecchi

Long after most chemists had given up trying, a team of researchers has synthesized the first ring-shaped molecule of pure carbon — a circle of 18 atoms.

The chemists started with a triangular molecule of carbon and oxygen, which they manipulated with electric currents to create the carbon-18 ring. Initial studies of the properties of the molecule, called a cyclocarbon, suggest that it acts as a semiconductor, which could make similar straight carbon chains useful as molecular-scale electronic components.

It is an “absolutely stunning work” that opens up a new field of investigation, says Yoshito Tobe, a chemist at Osaka University in Japan. “Many scientists, including myself, have tried to capture cyclocarbons and determine their molecular structures, but in vain,” Tobe says. The results appear in Science1 on 15 August.

Pure carbon comes in several different forms, including diamond, graphite and ‘nanotubes’. Atoms of the element can form chemical bonds with themselves in various configurations: for example, each atom can bind to four neighbours in a pyramid-shaped pattern, as in diamond; or to three, as in the hexagonal patterns that make up the single-atom-thick sheets of graphene. (Such a three-bond pattern is also found in bulk graphite as well as in carbon nanotubes and in the globular molecules called fullerenes.)

But carbon can also form bonds with just two nearby atoms. Nobel-prizewinning chemist Roald Hoffmann at Cornell University in Ithaca, New York, and others have long theorized that this would lead to pure chains of carbon atoms. Each atom might form either a double bond on each side — meaning the adjacent atoms share two electrons — or a triple bond on one side and a single bond on the other. Various teams have attempted to synthesize rings or chains based on this pattern.

But because this type of structure is more chemically reactive than graphene or diamond, it is less stable, especially when bent, says chemist Przemyslaw Gawel of the University of Oxford, UK. Synthesizing stable chains and rings has usually required the inclusion of elements other than carbon. Some experiments have hinted at the creation of all-carbon rings in a gas cloud, but they have not able to find conclusive proof.

One ring
Gawel and his collaborators have now created and imaged the long-sought ring molecule carbon-18. Using standard ‘wet’ chemistry, his collaborator Lorel Scriven, an Oxford chemist, first synthesized molecules that included four-carbon squares coming off the ring with oxygen atoms attached to squares. The team then sent their samples to IBM laboratories in Zurich, Switzerland, where collaborators put the oxygen–carbon molecules on a layer of sodium chloride, inside a high-vacuum chamber. They manipulated the rings one at a time with electric currents (using an atomic-force microscope that can also act as a scanning-tunelling microscope), to remove the extraneous, oxygen-containing parts. After much trial-and-error, micrograph scans revealed the 18-carbon structure. “I never thought I would see this,” says Scriven.

The IBM researchers showed that the 18-carbon rings had alternating triple and single bonds. Theoretical results had disagreed over whether carbon-18 would have this kind of structure, or one made entirely of double bonds.

Alternating bond types are interesting because they are supposed to give carbon chains and rings the properties of semiconductors. The results suggest that long, straight carbon chains might be semiconductors, too, Gawel says, which could make them useful as components of future molecular-sized transistors.

For now, the researchers are going to study the basic properties of carbon-18, which they have been able to make one molecule at a time only. They are also going to keep trying alternative techniques that might yield greater quantities. “This is so far very fundamental research,” Gawel says.

“The work is beautiful,” says Hoffmann, although he adds that it remains to be seen whether carbon-18 is stable when lifted off the salt surface, and whether it can be synthesized more efficiently than one molecule at a time.

doi: 10.1038/d41586-019-02473-z
References
1. Kaiser, K. et al. Science https://doi.org/10.1126/science.aay1914 (2019).

https://www.nature.com/articles/d41586-019-02473-z?utm_source=Nature+Briefing&utm_campaign=8838a84803-briefing-dy-20190819&utm_medium=email&utm_term=0_c9dfd39373-8838a84803-44039353

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