Energetics of Formation of Cyclacenes from 2,3‐Didehydroacenes and Implications for Astrochemistry

The carriers of the diffuse interstellar bands (DIBs) are still largely unknown although polycyclic aromatic hydrocarbons, carbon chains, and fullerenes are likely candidates. A recent analysis of the properties of n‐acenes of general formula C(4n+2)H(2n+4) suggested that these could be potential carriers of some DIBs. Dehydrogenation reactions of n‐acenes after absorption of an interstellar UV photon may result in dehydroacenes. Here the reaction energies and barriers for formation of n‐cyclacenes from 2,3‐didehydroacenes (n‐DDA) by intramolecular Diels–Alder reaction to dihydro‐etheno‐cyclacenes (n‐DEC) followed by ejection of ethyne by retro‐Diels–Alder reactions are analyzed using thermally assisted occupation density functional theory (TAO‐DFT) for n=10–20. It is found that the barriers for each of the steps depend on the ring strain of the underlying n‐cyclacene, and that the ring strain of n‐DEC is about 75 % of that of the corresponding n‐cyclacene. In each case, ethyne extrusion is the step with the highest energy barrier, but these barriers are smaller than CH bond dissociation energies, suggesting that formation of cyclacenes is an energetically conceivable fate of n‐acenes after multiple absorption of UV photons.