On-surface synthesis of a doubly anti-aromatic carbon allotrope

Abstract

Synthetic carbon allotropes such as graphene 1, carbon nanotubes 2 and fullerenes 3 have revolutionized materials science and led to new technologies. Many hypothetical carbon allotropes have been discussed 4, but few have been studied experimentally. Recently, unconventional synthetic strategies such as dynamic covalent chemistry 5 and on-surface synthesis 6 have been used to create new forms of carbon, including γ-graphyne 7, fullerene polymers 8, biphenylene networks 9 and cyclocarbons 10,11. Cyclo[N]carbons are molecular rings consisting of N carbon atoms 12,13; the three that have been reported to date (N = 10, 14 and 18) 10,11 are doubly aromatic, which prompts the question: is it possible to prepare doubly anti-aromatic versions? Here we report the synthesis and characterization of an anti-aromatic carbon allotrope, cyclo[16]carbon, by using tip-induced on-surface chemistry 6. In addition to structural information from atomic force microscopy, we probed its electronic structure by recording orbital density maps 14 with scanning tunnelling microscopy. The observation of bond-length alternation in cyclo[16]carbon confirms its double anti-aromaticity, in concordance with theory. The simple structure of C16 renders it an interesting model system for studying the limits of aromaticity, and its high reactivity makes it a promising precursor to novel carbon allotropes 15.