Cyclocarbons make up an emerging family of carbon allotropes, but their instability precludes the study of their physicochemical properties. We report a synthetic route to cyclopentenone-annulated [18]- and [24]dehydroannulenes that are stable aromatic and antiaromatic models of cyclocarbon precursors. Combining NMR spectroscopy, X-ray crystallography, optical spectroscopy, electrochemistry, spectroelectrochemistry, and density functional theory (DFT) calculations, we address the aromatic and antiaromatic behavior of these electron-accepting molecules. Cyclopenteno[24]dehydroannulenes undergo two-electron reductions to form Huckel-aromatic 26 pi-electron dianions with significant planarization. Replacing cyclopentenone corners with more electron-withdrawing cyclopentenediones lowers the reduction potentials, thereby enhancing the redox activity. Cyclopenteno[18/24]dehydroannulenes are designed so that each cyclopentenone corner bears a dimethylacetal group on the central carbonyl moiety. The chemical shift of the methyl groups acts as a probe for the aromaticity and antiaromaticity of the annulene system, confirming the diatropicity and paratropicity of the pi-conjugated system. The combination of structural control and electroactivity makes these scaffolds promising candidates for organic electronics and topochemical polymerization.
Funding Agencies|Villum Foundation [00040871]; Novo Nordisk Foundation [NNF24OC0090256]; Swedish Research Council [2022-06725, 2024-05286]; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoping University [2009-00971]; European Union (ERC) [101077649]